Name: Clark Kent
Relation: Best Friend
Portrayed by: Tom Welling
The friendship between Clark and Chloe was one of the longest and most significant relationships on the show. They met in the eighth grade, after Chloe and her dad moved to Smallville. Clark was the first friend she made on her first day at school, and later that same day they shared their first kiss with each other. Throughout their high school years Chloe harbored an unrequited love for Clark; he occasionally showed interest in pursuing a romantic relationship with her, but always refrained for fear of ruining their friendship. Chloe was eventually able to let go of her feelings for Clark and move on. Once she learned Clark's secret she became his most trusted ally, and their friendship grew even stronger. Throughout the years Chloe and Clark forged an unbreakable bond, becoming more like family than just friends. They've each proven time and again that they would go to any lengths to protect one another, and always would fight for each other's happiness.

Name: Lois Lane
Relation: Cousin
Portrayed by: Erica Durance
Lois and Chloe were first cousins, and lifelong friends. Lois first came to Smallville to investigate Chloe's apparent murder. She ended up enrolled at Smallville High with her cousin, and Chloe convinced her to write for the Smallville Torch. This was the beginning of Lois' career as a reporter, and Chloe can be credited for igniting the love of journalism in her cousin; for Lois would continue on to become a Pulitzer Prize winning reporter for The Daily Planet. Chloe is also to thank for being the reason that Lois meets Clark, who would become her husband one day. Although when Lois first arrived in Smallville Chloe showed some signs of jealousy, she never held any of Lois' achievements against her; instead she always supported and encouraged her cousin. And Lois' relationship with Clark was landmark for Chloe, as it was the first time she didn't try to discourage one of Clark's relationships out of jealousy or concern, she always supported them. And when Lois got cold feet before her wedding, it was Chloe who managed to convince her that marrying Clark was her destiny.

Name: Oliver Queen
Relation: Husband
Portrayed by: Justin Hartley
Chloe and Oliver first met when he dated her cousin, Lois. After meeting him, Chloe commented on how attractive he was, repeatedly saying "wow" to Clark. When she first heard of his superhero persona, Green Arrow, she admired his heroism and ideals. She eventually worked out that Oliver was Green Arrow on her own, and joined his team of superheroes, taking the codename Watchtower. Chloe and Oliver remained friends and colleagues through the years, while they both pursued other relationships. When Oliver lost sight of who he was, Chloe orchestrated an elaborate series of events to remind him that he was a good man, and a hero. He thanked her sincerely for saving him, which was a turning point for them, deepening their relationship. Eventually they both ended up single and spending a lot of time working together, and soon they were in a relationship. Since they had both been hurt badly in previous relationships, they tried to keep things "casual" at first. However, they began to fall in love with one another and so they decided to put their pasts behind them and move on together. Their relationship proved to be one of the deepest and most devoted in the series. Chloe sacrificed herself to save Oliver's life, and Ollie in turn remained faithful to her while she was gone. After they got magically intoxicated at Lois and Clark's pre-wedding party, Chloe and Oliver got married. When they realized this after sobering the next day, they both were happy and left to start a life together in Star City. They agreed that they would have married each other anyway, even without the spell.

Name: Jimmy Olsen
Relation: Ex-Husband
Portrayed by: Aaron Ashmore
Chloe first met Jimmy during her high school internship at The Daily Planet. He was also an intern, and they had a whirlwind romance that culminated in them losing their virginity to one another. Although Chloe expressed to Lana that sometimes regretted moving so quickly with Jimmy, she is nonetheless happy when she is reunited with Jimmy four years later, again at The Daily Planet. They began dating again, after they agreed to take things a little slower than they had the first time. However, their relationship was always rocky, due in part to Jimmy's jealousy of Clark. He couldn't understand Chloe's blind loyalty to him, no matter what inexplicable things Clark did; and Chloe in turn could never explain herself to Jimmy, because she had to protect Clark's secret. Although Chloe tried many times to reassure Jimmy of her love for him, he eventually breaks up with her. Things were strained between them for quite some time, but they eventually began to reconcile. They resumed their relationship after Chloe confessed her meteor infection to Jimmy; and after Chloe is attacked by Brainiac he proposed to her. She happily accepted, and even though their relationship continued to have some issues, they got married. The marriage eventually ended, however, when Chloe defended her new friend, Davis Bloome, from Jimmy. He saw it as a betrayal, and as yet another time that Chloe chose another man instead of him—an issue he continually had to deal with because of Clark. Chloe is heartbroken, but still kept the truth from Jimmy, even at the cost of their marriage. After Jimmy learned Clark's secret, he understood why Chloe had done the things she did and he forgave her. They reconciled, but only moments later Jimmy was murdered by Davis, leaving Chloe devastated.

Name: Lana Lang
Relation: Friend
Portrayed by: Kristin Kreuk
Lana was initially somewhat of a rival to Chloe, as Lana was always first in Clark's affections, making him blind to Chloe's love for him. Still they became good friends in high school, and developed a very close, sister-like, bond. Chloe even invited Lana to move in with her after Lana's aunt decided to move to Metropolis; and also included Lana on her family tree project at school, listing Lana as her sister. Chloe often named Lana as being her best friend (besides Clark) and they remained close friends through the years, even though they occasionally clashed—usually over Clark. Chloe was often jealous of Clark and Lana's relationship, although she tried her best to be supportive. And Lana was often insecure about Chloe and Clark's friendship, because he often shared more of his feelings with Chloe than he did with her. Chloe and Lana were roommates at Metropolis University, she was Lana's maid of honor when she married Lex Luthor, and she was also the first person Lana told when she thought she was pregnant. After Lana left Smallville, she and Chloe only saw each other rarely. But Lana did return to be a surprise guest at Chloe's wedding to Jimmy.