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Ainz Ooal Gown, originally known as Momonga, is the central protagonist of the story. His true name before entering the new world was Satoru Suzuki, an ordinary Japanese salaryman who lived a lonely and unremarkable life. When the MMORPG YGGDRASIL shut down, he was transported into that fantasy world permanently, inhabiting the avatar of his level one hundred undead magic caster, an Overlord. He is the guild master of the guild Ainz Ooal Gown, the supreme ruler of the Great Tomb of Nazarick, and the creator of the NPC Pandora's Actor. Physically, he appears as a skeletal figure devoid of skin and flesh, typically clad in an elaborate black academic gown trimmed with gold and violet.

As a human, Satoru Suzuki was kindhearted, socially awkward, timid, and diligent. In his new undead form, his emotions are automatically suppressed, making him appear cold, calculating, and detached. He retains a cautious and meticulous nature, always planning and controlling details, and he never underestimates his opponents, often employing overwhelming force to ensure victory. Because his emotions are dampened by his undead physiology, he no longer feels strong reactions such as fear, guilt, or grief, which allows him to commit ruthless acts without hesitation. Despite this, he still possesses a residual sense of human morality and occasionally questions the consequences of his actions. He is deeply loyal to the NPCs of Nazarick, viewing them as the children of his former friends, and treats them with a gentle and nurturing demeanor. He refrains from romantic involvement with any of them out of respect for the original creators.

His motivations are complex. Initially, he seeks to understand the new world and find a way to return home. Over time, he embraces his role as the absolute ruler of Nazarick and resolves to protect the tomb and its inhabitants at all costs. He also aspires to make the name Ainz Ooal Gown an eternal legend and to bring stability and order to the world by unifying it under his rule. Although his actions often result in destruction and cruelty, they are driven by loyalty to Nazarick and a pragmatic desire for survival and control rather than pure malice.

In the story, Ainz serves as the supreme commander of Nazarick, directing its conquest and expansion. He also adopts the alter ego Momon, a dark warrior and adventurer who becomes famous as the strongest adventurer in the land. This dual identity allows him to gather information and influence events from within human society. He is the Sorcerer King of the Sorcerer Kingdom, the nation he establishes after conquering the Re-Estize Kingdom.

Key relationships define his journey. Albedo, the Overseer of the Floor Guardians, is utterly devoted to him and deeply in love with him, though he remains emotionally detached from the romantic aspect of her affection. Demiurge is his most cunning strategist, whose loyalty is absolute and who interprets Ainz's often improvised decisions as parts of a grand master plan. Shalltear Bloodfallen, a powerful vampire, is fiercely loyal and serves as one of his strongest warriors. Sebas Tian is a noble servant who follows his own moral compass, and Pandora's Actor, the doppelganger creation of Ainz himself, serves as the overseer of the treasury. The Floor Guardians as a whole revere him as the highest of the forty-one Supreme Beings.

Ainz experiences significant development over the course of the story. He begins with uncertainty and anxiety about his new circumstances, but gradually grows more confident and authoritative in his leadership. As his undead nature suppresses his human emotions further, he distances himself from human morality and becomes more comfortable with the cold pragmatism required of a ruler. The gap between his internal uncertainty and the overwhelming confidence his subordinates perceive in him is a recurring source of dramatic irony.

Notable abilities include mastery of over seven hundred spells, making him one of the most powerful magic casters in existence. He wields several World-Class Items, legendary artifacts that can break the game's balance and grant immense power. His undead physiology grants him immortality, high resistance to many forms of attack, and an immunity to emotions such as fear. He commands a vast army of undead that can overwhelm entire kingdoms. Signature spells include Grasp Heart, which instantly kills weaker enemies with a crushing grip on their heart, Reality Slash, a spatial cut that bypasses most defenses, and Black Hole, which erases anything caught in its gravitational pull. Despite his overwhelming power, he is prone to overthinking strategies and relies heavily on the loyalty and capabilities of his subordinates.