Welcome to the 1800s
372 years had passed when in 1864 Katerina arrived in Mystic Falls, Virginia, by which time she had taken the name Katherine Pierce, presumably to avoid detection by Klaus. At some point she had become friends with Pearl and her daughter, Anna, and she saved the life of the witch Emily Bennett, putting Emily in her debt. Emily forged her a special piece of jewelry with the stone Lapis Lazuli which allowed her to walk in the sun without being burned. She was taken in by one of the town's founders, Giuseppe Salvatore, having spun a story about being orphaned by a fire that killed her family. Katherine met and fell in love with his son Stefan Salvatore, though she quickly began a physical relationship with Stefan's older brother, Damon, as well. Katherine created quite a few vampires while living in Mystic Falls, which inevitably alerted the Founding Families to their existence. Pearl warned Katherine that the town knew about the vampires after discovering an elixir containing vervain, which Honoria Fell had asked to be sold at the apothecary. Pearl tried to convince her to leave, but Katherine refused, claiming she had a plan in motion. Her plan, it turned out, was to turn Stefan and Damon into vampires, having seduced them both during her stay at the Salvatore household.
Realizing how quickly the Founder's Council would take action against the vampires, Katherine struck a deal with George Lockwood: she would give him the moonstone if he would help her fake her death. Eventually, Stefan unwittingly suggested to his father that he knew a vampire, and Giuseppe guessed Katherine's true identity. Giuseppe spiked Stefan's drink with vervain and, later that same night, Katherine bit him. She was incapacitated by the vervain in his bloodstream, and, hearing the commotion, Giuseppe burst in to take her away. Damon later went to rescue her, and Stefan, upset that he had hurt his brother and jeopardized Katherine's life, helped him in the effort. They were both killed trying to save her, shot by their own father, Giuseppe, who was ashamed his sons had succumbed to the wiles of a demon.
Katherine and the other vampires were taken to Fell's Church to be destroyed, but George helped Katherine escape. She gave George the moonstone, but instead of leaving right away, she turned to see Damon and Stefan's bodies lying in the road. She ran to Stefan, kissed him, and promised they would be together again someday. After transitioning into a vampire, Damon was told by Emily that Katherine was trapped in the tomb beneath the church, and as a result, the older Salvatore never stopped loving Katherine as he awaited the day he would be able to rescue her. In reality, Katherine was still lying low to evade Klaus, and she kept a close eye on the younger Salvatore brother, pointing out that she had seen him in the front row of a concert in the 1980s to prove that she'd always been watching over him.