Niki signed with BMA Records in 2005 and released her debut EP Pure Niki in the August of that year. She is also the author of several books, including Girlfriend Diary (周麗淇·女朋友手記; 2005), a book of the same title as her 2006 album The Child Woman (2006), Detailed Little Things (細味心事; 2007), Happiness (幸福; 2009), and Cherish (珍惜; 2010).
In 2006, she released Child-Woman and a single Nikikaka. In August 2010, she released a charity single Make a Wish with proceeds donated to an organization called Make-A-Wish Hong Kong.
She has twice won "My Favorite TV Actress" at the Astro Favorites Awards Ceremony.
Both series received high viewership ratings and Myolie soon rose to popularity.
In 2005, TVB aired five drama serials in which Myolie was lead actress.
In 2007, Myolie was paired with Mainland actor Feng Shao Feng in the TVB-CCTV joint production The Drive Of Life. She also starred as Chow Lai-Man in the second installment of War of In-Laws, Wars of In-Laws II in same year.
Myolie took another step in her acting career in 2009 by filming her first Mainland drama Beauty's Rival in Palace, in which she guest-starred in for five episodes and was once again paired with Feng Shao Feng.