Bell is Hestia's first Familia member and love interest. Hestia appears to have been in love with Bell since he first joined her Familia, as no one wanted to join her and the two were alone in the world. Hestia tends to get jealous very easily whenever Bell thinks about or interacts with other girls. Hestia also tends to sneak into his bed to sleep with him. Hestia worries about Bell's health and safety whenever he enters the dungeon.
Hestia has been shown to dislike Ais, namely because Ais is the reason for Bell's sudden growth in terms of strength and skills, as well as jealousy towards Ais' beauty. Hestia even stated that the reason she didn't tell Bell about his growth state was not only because others will be after him, but because of Ais, even stating it was ninety percent of the reason.
Hestia and Hephaestus appear to be very close friends, with Hestia even living with Hephaestus for a time, however, she was eventually kicked out by Hephaestus and told to find her own Familia. They were close enough for Hephaestus to create a weapon for Hestia's Familia member Bell Cranel. During a conversation with Welf, Hephaestus reveals that the reason the two are close friends is that Hestia was the only one to not laugh or mock her for her disfigured eye.
Hestia and Loki appear to have a rival goddess relationship that has lasted since the time they were in heaven until present. Loki tends to make fun of her small Familia as well as being a 'runt'. In return, Hestia makes fun of Loki's flat chest, much to Loki's chagrin. Their relationship is rather unfriendly, purposely keeping Bell and Ais apart from each other. While their relationship nears hostility, they do not appear to fight outside of verbal arguments, and Hestia even admits to one of Loki's virtues, that being her love for her children.
Hestia and Lili are rivals for Bell's affection, often clashing with one another over him. When first meeting Lili, Hestia was quite blunt on her dislike towards her, due to the fact that Lili had been cheating Bell out of his money. After Lili swore that would never do it again, Hestia then asked her to look after Bell and keep him out of trouble, to prove that she had changed with her actions. However, Hestia made it known that Bell was hers, to which Lili challenged.
Besides the topic of Bell, Hestia and Lili also tend to argue about other matters, like money. Despite this, the two do care for one another. When Lili surrendered herself to the Soma Familia, Hestia mounted a rescue, saying that Lili was essential to the War Game against the Apollo Familia. Furthermore, when Lili received a marriage proposal from Finn Deimne and looked inclined to take it, Hestia encouraged Bell to go after her. Similarly, when Bell said he would turn down a Goddess's love, causing Hestia to run off, Lili pointed out to him that he may have hurt her feelings if by the "off chance" she had feelings for a human.
Hestia and Welf have a good relationship. When Welf first joined Bell's battle party, Hestia encouraged Bell to keep him around, especially since it prevented him from being alone with Lili in the Dungeon. She supports him and his love for Hephaestus.
Hestia was initially very upset with Mikoto, as her Familia used a Pass Parade on Bell's party, trapping them in the Dungeon. She said that if Bell died, she would hold a grudge against them, but wouldn't hate them, and asked for her help in rescuing Bell. It seems her feelings towards her had subsided after the events on the eighteenth floor, as Hestia accepted Mikoto into her Familia in preparation for the War Game.
The two now have a good relationship. Hestia finds her cooking delicious and says Mikoto would make a good wife. She also supports her and her love for Takemikazuchi.
Hestia recognizes Haruhime as a rival for Bell's affection and gets angry whenever she sees the two of them being intimate. With Haruhime being more timid, Hestia tends to be the more domineering one. Nonetheless, the two have a good relationship. Seeing Haruhime and Wiene interact, Hestia admitted that she would make a good mother.
Upon first meeting Wiene, Hestia was stunned by her appearance. After hearing the explanation, Hestia decided to shelter her, as she couldn't turn her back on someone that was so afraid, and helped to give Wiene her name. Unlike some of the Familia, Hestia actively tried to become friends with Wiene, becoming slightly upset when Haruhime was able to do so before her.
Hestia shows a lot of care towards Wiene. After discreetly hearing her story while pretending to sleep, Hestia hugged her from behind. After Bell and the others returned from dropping Wiene off at the Xenos hidden village, Hestia was visibly saddened to not see her. Like her Familia, she was determined to save Wiene and the other Xenos when they were trapped on the surface. When Wiene wanted to save Bell from Ais, Hestia told her she would not stop her and remarked that she had grown strong.