Xu Hui started learning the guzheng at a tender age. She was admitted to the Shanghai Conservatory of Music. Under the tutelage of Associate Professor Guo Xue Jun, Xu Hui studied the guzheng, and concurrently studied percussion under Professor Yang Ru Wen. During her course of study, she was awarded scholarships for four consecutive years. She is currently a Guzheng Associate Principal and Percussionist with the Singapore Chinese Orchestra. Xu Hui is a guzheng instructor at the Nanyang Academy of Fine Arts and she is also in the Executive Committee of the Singapore Qinzheng Association.

Xu Hui was the champion at the 1992 International Jiangnan Sizhu Competition. In the same year, she won the first prize at the Shanghai Young Talents Guzheng Competition. Xu Hui was also the first-prize winner at the Eastern China Youth Chinese Music Competition for two consecutive years. In addition, she was awarded a silver medal at the National Cultural Stars Award in 1995.

Xu Hui has staged many performances throughout Asia, Europe and America. She has performed numerous guzheng concertos which include: Midnight at the Maple Bridge, Wind of Falling Plum Blossom, A Peacock Southeast Flew, Desert Dust, Mountains and Water, Dunhuang Tang Ren Wu, Three Characters Classics Capriccio and more. Xu Hui has also performed and staged 3 solo guzheng recital concerts at the Esplanade — Theatres By the Bay. Xu Hui has also collaborated with many renowned musicians and composers and her performances have received well acclaims.

In terms of teaching, Xu Hui has inspired her students to achieve excellence, with many of her students winning various accolades from local and overseas competitions, such as the Singapore Chinese Music Competition (previously known as National Chinese Music Competition), Nanyang International Music Competition and Eastern China Youth Chinese Music Competition.