Li was most recently country executive and head of global banking for China at RBS, Australia's No 4 bank said in a statement, replacing Christine Ip who quit and moved to Singapore late last year.
"Since establishing our locally incorporated entity last October we have increased the pace of our expansion," ANZ's China Chairman Gilles Plante said in a statement.
ANZ runs its own operations in China and also owns a 20 percent stake in the unlisted Bank of Tianjin and Shanghai Rural Commercial Bank.
Separately, Ip has joined Singapore's No 3 lender United Overseas Bank as its senior vice president for the Greater China region, two sources with direct knowledge of the information said on Thursday.
Ip's appointment points to a stronger push by UOB to expand its operations in China outside of its Singapore home market, one of the sources said. The two sources declined to be named because the information was not yet public.
The former HSBC and Standard Chartered banker had previously helped ANZ receive approval from the Chinese authorities to incorporate locally in the country, and was crucial in the bank's China expansion drive.
UOB was not immediately available for comment.
Competition for experienced financial talent has been intensifying in recent years, with bankers frequently moving between firms as new players seek to gain a slice of the fast-growing China pie.