On the September 22, 2006 episode of SmackDown!, Ouellet, known as simply Maryse, was shown on the TitanTron welcoming the Montreal viewers (in French) to the season premiere of SmackDown! on the CW Network. Maryse made her first actual television appearance with her entrance theme on the May 21, 2007 episode of Raw to present American rapper Timbaland's new music video for the single "Throw It on Me" (2007), in which she had appeared.
By the time she began appearing regularly on SmackDown at the beginning of 2008, she had adopted a snobby attitude, thus becoming a villain in the process. On the March 7, 2008 episode of SmackDown, Maryse competed in a swimsuit contest, against Victoria, Michelle McCool, Cherry, and Eve Torres. In the end, Maryse and Eve got into a fight. On March 14, Maryse was the first eliminated from the swimsuit competition. On March 28, Maryse competed in a "Wet and Wild" match where she teamed with Victoria against Cherry and McCool in a losing effort. On a "SmackDown after the bell video" on WWE.com, the tag team, Deuce 'n Domino dumped Cherry (who had been their manager) and replaced her with Maryse. Maryse then insulted Cherry, only for Cherry to slap her. On the May 16 episode of SmackDown, she made her television in-ring debut in a losing effort to Cherry, though defeated her in a rematch with a roundhouse kick weeks later. For weeks, Maryse teamed with Victoria and Natalya against Cherry, Michelle McCool and Maria. Maryse then suffered a minor broken nose after receiving a bulldog from Maria.Maryse lost in her first title match for the WWE Divas Championship against Michelle McCool at Unforgiven in September, resulting in a feud between the two Divas. She then came up short once again in title rematch on SmackDown. On the September 23 episode of ECW, Maryse defeated McCool in a non-title match. After being off television for a month, Maryse returned at November's pay-per-view event Survivor Series to participate in the five-on-five SmackDown vs. Raw Divas Elimination match. Maryse was the sole survivor of the SmackDown team, but ultimately was eliminated by Beth Phoenix. On December 19, Maryse pinned Maria to become the number one contender for Michelle McCool's Divas Championship. The next week on SmackDown, Maryse beat McCool to become the new Divas Champion in a match with Maria as the special guest referee. On December 28, 2008 at a house show in Raleigh, North Carolina, Maryse dislocated her knee in a tag team match against The Bella Twins, when one of the twins initiated a dropkick that landed on her kneecap, it was later announced that the injury was not too serious and that she would be able to return in a few weeks. On the January 23, 2009 episode of SmackDown, Maryse returned in a non-wrestling role and sat at ringside commentating, during a Divas' tag team match. Maryse returned to wrestling on February 20 in a tag team match with Michelle McCool and defeating Maria and Eve Torres. On April 5, Maryse competed in a Divas battle royal at WrestleMania XXV, but the match was won by Santino Marella.On the April 13 episode of Raw, Maryse was drafted to the Raw brand as part of the 2009 WWE Draft, in the process making the Divas Championship exclusive to the Raw brand. She made her Raw in-ring debut on April 27, teaming with Beth Phoenix, Rosa Mendes, and Jillian Hall in a loss to Mickie James, Santina Marella, Brie Bella and Kelly Kelly. At the Night of Champions pay-per-view on July 26, Maryse lost the Divas Championship to Mickie James. She then took a hiatus from WWE to recover after having knee surgery. Maryse made her return on the November 23 episode of Raw, disguised as The Gobbledy Gooker, as the guest timekeeper for a divas tag team match. After the match, she revealed herself by attacking Melina. The following week, Maryse made her in-ring return on the November 30 episode, pinning Melina in a tag team match.