WWE's website announced on June 1, 2006 that Massaro would be the newest SmackDown! diva. She made her debut on the June 2, 2006 edition of SmackDown! as a special guest commentator during the Kristal Marshall vs Jillian Hall match. Upon debuting on SmackDown!, Massaro aligned herself with Jillian Hall as they feuded with Michelle McCool and Kristal Marshall. She won her debut match on the July 21, 2006 edition of SmackDown! where she teamed up with Hall and defeated McCool and Marshall. At The Great American Bash 2006, Massaro won the Fatal Four Way Bra and Panties Match. On the August 4, 2006 edition of SmackDown!, Massaro broke her knuckle in a match against Kristal Marshall. On August 16, 2006 she hosted

Ashley returned to the ring on the September 9, 2006 edition of SmackDown! where she, Paul London and Brian Kendrick defeated Idol Stevens, K.C. James and Michelle McCool in a Six-Person Mixed Tag Team Match. Following the victory, Ashley became the manager for London and Kendrick, accompanying them to the ring for their matches on SmackDown! and PPVs. Ashley competed in the first ever Extreme Strip Poker segment on ECW on October 10, 2006 representing SmackDown!.

During the February 16, 2007 edition of SmackDown!, Ashley unveiled her Playboy cover. Surrounding the release of the magazine, Ashley engaged in a feud with Jillian Hall over who was the most talented Diva on Smackdown! and Hall's jealousy over Ashley's Playboy cover. At No Way Out 2007, Ashley won the first ever Diva Invitational by removing her top to reveal her breasts which were covered Playboy bunny pasties.

Surrounding the release of the cover, Ashley continued to feud with Jillian, but also began a feud with WWE Women's Champion, RAW's Melina. Melina was angry over the publicity Ashley had been receiving because of the cover and believed that she deserved more publicity than Ashley for being the Women's Champion. At WrestleMania 23, Melina defeated Ashley in a LumberJill Match to retain her title. Shortly before Wrestlemania 23, Ashley would become the valet for WWE Tag Team Champions Brian Kendrick and Paul London.