During the later years of the First Age, Huan was involved with the Quest for the Silmaril. When Beren Erchamion had left Lúthien, and gone with Finrod Felagund to Angband but had been captured in Tol-in-Gaurhoth, Lúthien set out to rescue him. However, Huan smelt Lúthien and captured her, and she was brought before Celegorm. Celegorm and Curufin did not reveal to her that they had sent Beren to his death by the hand of Sauron, and took her as a prisoner to Nargothrond, "for her own protection", secretly plotting to wed her to Celegorm and thereby force an alliance with Lúthien's father Thingol.
Huan felt pity for Lúthien, and sought her out. Speaking for the first time, he told her of a way to escape, and then accompanied her to Tol-in-Gaurhoth where, with the help of Lúthien's magic, he killed all of Sauron's wolfhounds until Sauron himself came out, knowing of the prophesy about Huan's death he took the shape of the greatest wolf that had ever lived up to that point. Huan fought against Sauron and defeated him in single combat. While Lúthien and Beren went on their way back to Doriath, Huan went back to his master until he learned that Celegorm and Curufin, who had been exiled from Nargothrond by Orodreth. When Curufin tried to kill Lúthien, Huan turned against his master, defending Beren and Lúthien.
Speaking for the second time, Huan told Beren and Lúthien of his plan to gain entrance to Angband, bringing them the skin of the Wolfhound Draugluin and the bat-skin of Sauron's messenger Thuringwethil. Using these skins as disguise Beren and Lúthien went to Angband, while Huan hunted in the wild. After Beren and Lúthien had won the Silmaril but Beren had lost his hand to the wolfhound Carcharoth, Huan quickly rushed to help him, Thingol, Beleg Cúthalion, and Mablung in the Hunt for the Wolf. Huan and Beren managed to kill Carcharoth, but Huan was mortally wounded. Speaking for the third and last time, he wished Beren and Lúthien farewell, and died.