Jessie Caine is a singer-songwriter who previously resided in Nashville and has recently returned to town.
Introduced in the Season Five episode (Now and Then There's) A Fool Such as I, she is a former Nashville native who has recently returned to town after some time away. She performs at an open mic night at The Bluebird Cafe and afterwards talks to Deacon about Rayna.
In the episode Ghost in This House, she meets Zach Welles at the Highway 65 offices and is interested in signing with the label. Zach has a word with Deacon, telling him that she was previously married to label boss Brad Maitland, and when she meets up with Deacon they talk about previous relationships but when he phones her after she contacts him about her showcase she believes he is romantically interested in her but does not feel the same way and hangs up on him. He later shows up at her showcase but leaves when her song hits an emotional cord with him.
She attends at charity fundraiser in the episode The Night Before (Life Goes On) and switches Deacon's name card to another seat as she does not want to sit next to him. However, when her ex-husband arrives and starts commenting about their son, Deacon sees how uncomfortable she is. They encounter each other outside and she starts talking about her son and how Brad tried to turn him against her.
In the following episode, Deacon tells her that Scarlett had a miscarriage and Jessie decides to leave over some items to Scarlett's house before the latter invites her in for coffee. Jessie reveals that she had several miscarriages over the years so she knows what Scarlett is going through. Deacon later introduces her to Maddie and Daphne.
She does not have an easy time with her ex-husband being in town since he is making life hard for her, saying she is in breach of the court order in regards to their son. When Deacon faces trouble with Highway 65, she brings him to the lake so that he can take time to figure out things for himself. After performing at the Opry, Daphne sees them hug and begins to worry that Deacon may be moving on too fast but Deacon reassures her that she and Maddie are the two most important women in his life.