When she learned that Harkon intended to use her daughter Serana's blood as part of a ritual to darken the sun, she hatched a plan. She cares less about his plans for extinguishing the sun than she does about seeing him humiliated. She has always been at odds with her husband, Harkon, and his methods. Valerica is one of the Daughters of Coldharbour, women who ritually sacrifice themselves to the Daedric Prince Molag Bal and receive the power of vampirism in exchange. Upon Harkon's death, Valerica was finally able to leave the Soul Cairn and returned to Castle Volkihar.
While Lord Harkon still somewhat cared for Serana, he has no remaining respect for his estranged wife. To stop him, Valerica sealed herself and the Elder Scroll inside the Soul Cairn, and hid away Serana, as well, so Harkon could never complete his ritual with their blood. He required the blood of a true Daughter of Coldharbour to power Auriel's Bow, and he had the option of using either Valerica or Serana's blood. Valerica, Harkon and their daughter Serana had a falling out as Harkon became determined to blot out the sun forever. After Harkon made a deal with Molag Bal to become Vampire Lords, Valerica gained the honorary title of Blood Matron of Castle Volkihar. Valerica was the castigated wife of Lord Harkon, leader of the Volkihar clan.