Hiei is a half fire, half ice demon, born from a race of Ice Maidens who reproduce asexually once every 100 years. The Ice Maidens lived on a floating island, cut off from the rest of the demon world. Since she was born because her mother had an 'interaction' with a fire demon, she was cast off the island and left to die.
She survived being cast from the floating island and grew up with a band of demon bandits. She became a fearsome demon, never hesitating to taunt and kill anyone that got in her way. As she grew up, she killed demons for fun and sport, using the tear stone that she was given at birth to lure other demons into attacking.
Later on in her life, she received the Jagan implant from the demon surgeon Shigure in return for telling the story of her life up until then. She was warned that the surgery would be very painful and would take away a lot of her strength. She accepted the terms anyway, knowing that she would go from being an A-class demon to that of a lower D-class demon. In order to survive, she stayed to learn swordsmanship from Shigure. While staying with the surgeon, she decided to use her new Jagan for the original reason that she wanted it for, to search for the Ice Maidens that had cast her out as a child. She also wanted to find the Tear Stone that was given to her as a baby that she had lost in a fight with another demon.
After setting out on her journey, she arrived back at the village in a matter of days. Instead of finding her mother, she found Rui, who told her that her mother had committed suicide because of the depression and guilt of witnessing her other daughter's 'death'. Rui begged for her own death and that of the other Ice Maidens, but after a few minutes of thought, Hiei refused and walked away. She also learned of her twin sister, Yukina, from Rui.
After her visit to the Ice Maidens' Hiei decided to use the Jagan to watch over her twin sister instead of finding her Tear Stone. During her talk with Rui, she had learned that Yukina had left the village in order to seek out her lost twin sister. When she left Shigure as a payment for his lessons as a swordsman, she agreed never to tell Yukina that she is her twin sister.
She spent many years searching for her twin sister, Yukina and her search eventually took her to the human realm. There she meet Youko Kurama, using the human form of Suichi Minamino. A year after their first meeting, Hiei helps steal three artifacts from the demon world along with Kurama and the demon Gouki.
When Kurama walks out on them, she is furious and then disappears, leaving Gouki to fight Yusuke. After Gouki's defeat and after Kurama gives up, Hiei fights Yusuke herself and looses. Two weeks later, she helps him out with his third case, doing her part to help defeat the Four Saint Beasts, killing Seriyuu. During Yusuke's fourth case-to rescue Yukina- she had to deliver the video tape with Yusuke's orders to him. She was given this task because if she knew the details of the mission, she would surely kill the human holding Yukina hostage. If she would have done that, she would have been punished severely because it is forbidden for demons to kill humans.
She found out the details anyway and nearly killed the man holding her sister hostage, but she thought Yukina's life was worth more and that he wasn't even worth killing. Afterwords, Yukina said that she looked familiar to her, but true to her word, she didn't tell Yukina that she was her twin sister.
Several months later, during the Dark Tournament, she was able to master the flames of the demon world, but when she first used it, it crippled her arm. Later on, during the third round of the tournament, she was tricked into being held behind a force field, which had an odd affect on her crippled arm, it healed it back to 100%.
During the final round of the tournament, she was able to master the fires of the demon world, consuming it to give herself even greater strength. She beats Team Toguro's Bui with this new technique and also destroys half of the stadium in the process.
Sometime after the Dark Tournament, Hiei refuses to help Yusuke and the others against Shinobu Sensui, who wants to open up a portal to the demon world. After saving Yusuke from Sensui's 'Sniper' she fights him to calm him down, since he was enraged over Kuwabara's kidnapping. Eventually, she is caught in another dimension with Kuwabara and Kurama and is forced to watch Yusuke fight against Sensui.
After Yusuke's death, she regains some of her old power, but that isn't even enough to stand up against Sensui's S-class sacred energy or Yusuke's new demon powers. After Sensui's death, she is given a bribe, the Chapter Black tape, which has all the crimes humans have done against themselves and others because of her help in Sensui's defeat. She destroys the tape without watching it.
Hiei eventually returns to the demon world to join Mukuro's army. She survived a harsh, six-month survival test to become a member of her inner circle. Her final match was against the demon surgeon, Shigure. Sacrificing her arm, she defeats him. After the fight, she was restored back to normal and given her Tear Stone back. Mukuro had been the demon to find it after she had lost it. After the death of one of the demon lords, she travels with Mukuro to meet up with Yusuke.
After Yusuke announced his idea for a demon world tournament to decide the next ruler, she decided to fight as well. She is on her way to the tournament when she finds herself in Toshima.