The episodes feature two main characters: Rhys, a Hyperion business shark and Fiona, a tough-as-nails con artist. They have vastly different personalities but their circumstances force them to work together. How they and other characters in the story react is up to the player. Every choice made and everything they say is remembered by other characters and can influence later events.
There are a total of five episodes in the adventure, each with their own release date.
Chronology-wise, events of Tales from the Borderlands are unreliably narrated by Rhys and Fiona roughly a year after they actually happened. Relative to overall timeline, episodes 1 to 3 take place some time after events of Borderlands 2, just right before The Pre-Sequel's prologue and epilogue, and remaining are set shortly after that.