The two initially met in the Season 6 episode "Bloomix Power" as Daphne searched for a book containing information on Treants in the Alfea Libraries. While the two of them were shy towards the other, the two hit it off well after Thoren helped her uncover the Treants' weakness after admitting to a fear of his due to a bedtime story his father always told him as a child. By the end of the season, the two are married despite having been together for the shortest amount of time out of all the known couples.
As mentioned before, Daphne and Thoren first meet each other in the episode "Bloomix Power." As the Winx, Specialists and Nex train in the Alfea Gym, Daphne searches for clues on how to defeat the Treants in the school's library.
As she does so, Thoren comes by holding a book containing an old story about the Treants that his father used to tell him every night as a child believing that it could help her. When Daphne reveals that she is looking for a way to defeat them, Thoren unknowingly gives her the answer she had been seeking by insisting that if anyone could get to the root of the problem, it would be her. Realizing this, Daphne rushes out to the courtyards to meet with the others and form a plan.
As Bloom tries to hide the pain she had been feeling ever since she gave up sparks of her Dragon Flame to the Winx to help restore their powers, she catches a glimpse of Thoren and Sky wandering the royal palace. Thoren asks Sky if Bloom had said anything about him to Daphne, only to be ignored by his cousin, until Bloom calls out to them. In response, Thoren greets Bloom and accidentally blurts out the fact that he and Sky were just talking about her and her sister while Sky, who appears to be growing increasingly annoyed with Thoren, simply remains silent.
Once the ceremony for Daphne's coronation commences, Bloom and Daphne present themselves to their guests in the party hall. Bloom notices how much Thoren seems to have been staring at Daphne and playfully tips her sister off to her not-so-secret admirer, but Daphne does not do much in response and carries on with the ceremony.
After Daphne is officially crowned as next-in-line for the throne, everyone moves to the ballroom to dance. Thoren asks Daphne to dance, which she accepts and, as the two of them dance, Bloom meets up with Sky to talk about how happy she is to see her sister enjoying herself. Sky, however, warns Bloom to keep Daphne away from Thoren as he thinks of Thoren as nothing more than a dirty coward for abandoning him during their childhood when they were attacked by a group of Yoshinoya's ninjas.
Though their day out is going well, Daphne remains worried about Thoren and confesses to Bloom that she has been unable to tell how he truly feels about her even when he is always nice to her, which prompts Bloom into telling Daphne to trust in her heart as Thoren's behavior around her proves his love for her more than words ever could.
After their little talk, Daphne and Bloom regroup with Sky and Thoren, where they get acquainted with Breeze, the Champion of Gardenia, according to Sky. Almost immediately, Daphne and Breeze take a liking to each other, much to Thoren's surprise, and he uses their quick attachment as "proof" that shows how irresistible Daphne is to those around her.
The two of them are seen again once the Centaurs are summoned to wreak havoc at the Horse Fair by Selina. As the Winx hurry to protect the panicking fair-goers, Daphne helps to evacuate them as Thoren helps Nex and the Specialists keep the Centaurs at bay.