Their relationship is first shown in the episode Smarty Pants. Alex has a crush on Dean; he appears to like her as well. Dean finally finds out that Alex has a crush on him in Graphic Novel. Alex is determined to find out if Dean likes her in the episode Racing.
Towards the end of the episode, they become a couple. In Alex's Brother, Maximan, they go on their first date, but Alex is scared, because Dean asks her to meet him in a corner where he kisses girls. Even though she is scared, she goes, but she gets angry that he did not even try to kiss her and askes him for the truth. He said that every time he kissed a girl they would run off to tell their friends and that he did not want that to happen again.
Alex promises that she won't run off, and they have their first kiss. Later, in Saving WizTech, Part 1, Dean goes into a gelle because of a spell Ronald Longcape Jr. performs. Ronald (who used magic to impersonate Dean) breaks up with Alex. Near the conclusion of Saving WizTech, Part 2, Alex manages to save him. But, in Wizards vs. Vampires: Dream Date, Dean moves away to Ohio, so they grow apart and break up. However, he comes back in Journey to the Center of Mason and wants to get back with Alex, but she refuses, because she is still in love with Mason. Dean greets Alex by saying, "Hey, Russo." In the episode Saving WizTech, Part 2, Dean begins to call Alex by her first name.