Backstory: Being the daughter of Cinderella and Prince Charming, Chloe had learned a great many skills far beyond that of just being a royal. She has learned to respect people, no matter what their background, and to always be honorable. While she is the younger sister to Chad Charming, she does tend to be quite a bit more intelligent than he is, not just relying on her looks to get her through life she wishes to be an independent woman. She first met Red when she was freed from The Isle of The Lost, where all the villains of their parents past stories were kept imprisoned before having children of their own.
At first she and Red don't really hit it off too well, but as she comes to realize that Red is not all that bad, that she has potential and is fighting to see the good in herself, Chloe had become friends with her, and fights to help her when and where she can. Rather devastated when she up and disappears, only for the concerns to grow in volume when Queen Mal herself disappears within a cloud of smoke. Certain that one of their villains from the isle are responsible she is ready to team up with King Ben, Evie, Jay and Carlos to find who is responsible.
Facts: You can use the movie as reference for the relationship Red and Chloe have, just know that there is no Queen of Hearts, there is only a King of Hearts, and there is no travel back in time to make things right (no her mother is not sentenced to death either)