The series explores the pasts and motivations of key characters such as Connor, whose backstory involves a damaged reputation due to his vampire theories, and who finds purpose and redemption by joining the Library full-time. Vikram Chamberlain, considered possibly the worst Librarian ever from the past, is brought into the present day and must adapt while working with a new team. Charlie is a mysterious team member with a troubled past and regrets, whose development is a focus in early episodes. Lysa is revealed to be a descendant of Anya, which ties into the story's mythology and her role in stopping threats like the Drekavac.

The show layers current zeitgeist elements into its narrative in a digestible way, making characters relatable by having them face real-world problems alongside magical adventures. This approach allows escapist entertainment to resonate emotionally, as characters themselves are escaping their own issues, which in turn provides viewers a way to escape their problems through the story.

The Drekavac is a deadly threat introduced early in the series, with Lysa and Connor being in the right place at the right time to stop it from killing anyone in Belgrade. This event ties into the characters' destinies and the message that everything happens for a reason, setting the tone for the team's mission and the unfolding story.

The new team is brought together under unique circumstances, with Vikram from the past joining forces with new Librarians and their Guardian. Unlike previous teams, some members like Charlie are initially uncertain fits, having been thrust into missions unexpectedly, which creates tension and opportunities for character growth. The team’s chemistry and individual backstories are explored to establish a fresh yet familiar dynamic.

Key mysteries include the full extent of Charlie's past and the reasons behind her regrets, the deeper implications of Lysa's lineage as a descendant of Anya, and the true nature of Vikram's reputation as the worst Librarian ever. Additionally, Connor’s past and how it shapes his present role remain a compelling thread, with the series gradually revealing these elements to deepen character development and plot complexity.