Mr. Puzzles is the charismatic leader of the group and the emotional center of the series. He has a television for a head with expressive digital eyes, a sharp smile, a purple suit with yellow accents, and an old-fashioned showman appearance that makes him look like he's constantly hosting his own broadcast. He's theatrical, manipulative, dramatic, and obsessed with entertaining people, often treating everyday situations like they're part of a TV program. Unlike his SMG4 days, he's no longer chasing fame through PUZZLEVISION—instead, he's trying to figure out who he is after losing everything. That internal conflict between becoming a better person or slipping back into villainy becomes his biggest challenge.

Mr. WPNZ is Mr. Puzzles' closest companion and the deuteragonist of the pilot. He has a rugged, action-hero-inspired design with a darker color palette that contrasts Mr. Puzzles' flashy appearance. He's energetic, sarcastic, practical, and much more grounded than Puzzles, often acting like the teammate who keeps the group moving when everyone else gets distracted. His partnership with Puzzles is built on surviving the aftermath of the previous era together, and their chemistry mixes buddy-comedy banter with genuine loyalty as they step into an unfamiliar world looking for purpose.

The Pink Thing is intentionally mysterious and probably the strangest member of the cast. Its bright pink, book-like appearance makes it stand out immediately, and its name suggests it's meant to feel bizarre rather than conventionally threatening. The promotional material gives away very little about its past, but its unsettling, unpredictable vibe makes it seem like the wildcard of the group—the kind of character whose odd behavior could be either hilarious or surprisingly dangerous.

Lord General has the most imposing design of the newcomers, wearing armor and military-inspired clothing with fiery red and black colors that make him look like a battle-hardened commander. His personality appears stern, disciplined, and intimidating, carrying himself with the confidence of someone used to giving orders, but when someone is nice to him and he’s nice back, he throws a massive tantrum and says terrible things in the world to make himself more evil. Rather than being a chaotic villain, he seems to represent organized power, suggesting a history of commanding armies or leading large-scale conflicts before becoming part of Puzzles' growing villain circle.

Lady Killer is introduced as one of the new villains joining the cast. Her insect-like appearance gives her a sleek assassin aesthetic, with long limbs, sharp features, and a design built around agility rather than brute strength. She comes across as cool, confident, and calculated—the type of character who seems comfortable staying one step ahead of everyone else. While her full backstory hasn't been revealed, the promotional material frames her as a deadly professional whose skills add a stealth-focused dynamic to the team. She does not speak at all but she does love giving motivation stickers to the people she likes or just as a weapon.

The Big Bad is the central antagonist of Calling All Villains and the mysterious figure responsible for organizing the villain competition. They hold the prestigious position of the greatest villain in the galaxy and announce a competition to find someone worthy of inheriting their title. Their influence and authority establish them as a significant figure in the villain community, bringing together various aspiring villains, including Mr. Puzzles and his companions. Their personality is relatively mysterious, but they come across as an imposing and powerful individual whose decisions determine the direction of the competition. Their English voice is provided by Skuba.

Little robots who explode as soon as their purpose is fulfilled. They all have different voices and when exploded, bones and oil fly everywhere.