Famous for his Star Award-winning performances on the Singapore MediaCorp Channel 8 programs Bountiful Blessings, Unriddle 2, and Stepping Out, Hui is also known for his Star Award-nominated roles on My Home Affairs, Mars vs. Venus, and numerous other Mandarin-language series.
After serving in the Singapore Armed Forces, he earned a bachelor's degree in political science and economics from the National University of Singapore. Before beginning his acting career, he also worked as a Subway sandwich company manager.
A singer as well as an actor, he won a Star Award for his performance of the Honour and Passion theme song "Follow Me."
He grew up in Singapore in a family of Han Chinese (Hokkien) ancestry. In 2010, he married his university professor girlfriend.
He and Chinese actor Qi Yuwu both appeared on the popular television series C.I.D.