It was also during those years that Myleene got work singing back vocals for Cliff Richards, k.d. lang, and Michael Crawford, with whom she spent two months on tour. Next for her was the Royal Academy of Music. Even though she had no university degree, they listened to her music and took her on as a post-graduate student. In January 2001, the British network ITV was launching a new TV show called Popstars, in which a nationwide talent search would allow the public to vote to form a five-member pop group. Each week, millions of viewers tuned in to watch the auditions. Myleene was interested in the idea and submitted herself to this grueling process. The group of hundreds of hopefuls was brought down to 60 and finally to 10. The young musician from Norfolk managed to hang on for the ride. Finally, the votes were in and the final five were chosen. They were Noel Sullivan, Kym Marsh, Suzanne Shaw, Danny Foster, and, of course, Myleene Klass. The band would eventually be named Hear'Say.

At the same time, Myleene was offered a classical record deal, but she turned it down as she didn't feel she could commit herself to both. She wanted to give herself wholeheartedly to her new band. Before their first album, Popstars, was released in March 2001, Hear'Say was already one of the greatest cultural phenomena the United Kingdom had ever seen. Their debut single, "Pure and Simple," sold over 1.2 million copies and they were on top of the world. It was the fastest selling single in UK chart history. In July 2001, they released a second album called Everybody. However, after singles like "Lovin' Is Easy," "I Knew You Were Waiting," and "Way to Your Love Pt. 1," the British public soon grew tired of the endless tabloid articles on them and their numerous TV interviews.