Hestia serves as goddess and leader of the Hestia Familia, guiding its sole adventurer member, Bell Cranel. Residing with Bell beneath an abandoned church, she works part-time jobs to sustain their daily needs. Deeply protective, she initially conceals Bell's rare rapid-growth skill, fearing potential repercussions if discovered. While harboring romantic feelings for him, she understands Bell sees her as family and remains steadfastly committed to his growth despite this unreciprocated affection.

During Orario's Holy Moon Festival in the Arrow of Orion events, Hestia encounters her old friend Artemis. Their reunion sours as Artemis takes immediate interest in Bell, calling him "Orion." Hestia reluctantly joins Artemis' quest to defeat the monster Antares after a magical spear chooses Bell. On the journey, Hestia voices frustration with Artemis' conduct and vague accounts of her Familia's disappearance.

Hestia confronts Artemis about her true motives, growing increasingly suspicious of the mission, especially upon learning the spear is lethal. She attempts to discard it to prevent its use against Artemis. When Antares is revealed to contain Artemis' crystallized form, Hestia witnesses Bell's despair upon realizing he must kill Artemis. Her heartfelt pleas help Bell regain resolve to save Artemis rather than destroy her. Following Artemis' sacrifice and reincarnation, Hestia comforts the grieving Bell, showing him how his actions restored the surrounding forest.

Her actions consistently prioritize Bell's well-being, navigating complex divine relationships and moral challenges throughout this mission.