Li replaces Xing Hu who left the group in March "to explore new professional opportunities", the firm said.
She will be based in Hong Kong and will report to Thomas Gerhardt, head of emerging equities and commodities.
Philippe Uzan, CIO of long-only management at Edmond de Rothschild Asset Management (France), cited "the gradual opening up of the Shanghai and Shenzhen stock markets and China's position as the second largest market in the world in terms of market capitalisation", as a key opportunity for the China equities team.
Li has 18 years experience in finance in London and Hong Kong. She joined Edmond de Rothschild Asset Management (Hong Kong) in 2011 as a senior fund manager.
Prior to that, she was an Asia specialist at Altima Partners from 2007 to 2011. She had previously been a fund manager focused on China at Fabien Pictet & Partners in London.
The Edmond de Rothschild Group, which specialises in asset management and private banking, had €136 billion of assets under management at the end of last year. Of that total AUM, asset management accounted for about €49bn.