Kris is the main character in Deltarune. You play as Kris during exploration, puzzle solving, and combat. Although there are times where you select combat moves for Susie and Ralsei as well.
Susie is one of the playable characters in Deltarune, who tags along with Kris into the Dark World in Chapter 1. She is occasionally playable during many of the combat sequences, and is part of your party for the majority of Deltarune.
First appearing as a hooded figure, Ralsei reveals himself as a prince. Except he hasn't had any subjects for a long time. He's just been waiting for you and Susie to appear. Ralsei doesn't believe in fighting and will always encourage you to use your Act move instead of Attack.
Lancer is your first enemy and plays a large role in the story. You'll see him for the first time in the mysterious Underground but that definitely won't be the last. Lancer is the King's son.
The King of Deltarune is the main antagonist of Chapter 1 and serves as the final boss. He is the father of Lancer.
Rouxls Kaard heads up puzzles for the Darkeners. You will have to solve a few of his puzzles in the Castle.
Jevil is the Prisoner you have the option to free. He serves as a hidden boss battle.
Seam is the shopkeeper located towards the end of the Field. You can purchase and sell several items from them.
Toriel is Kris and Asriel's mom. She's also a school teacher in town.
We never see Asriel. We only hear about him. This is Kris' older brother who is away at university.
Alphys is Kris' teacher in school and also appears as one of the references to Undertale.