Michael Evans, who was a partner for 20 years with the US-based investment bankers, has been an independent director of the Chinese firm since Alibaba's initial public offering (IPO) in September last year.
His appointment "highlights Alibaba Group's strong commitment to globalising its business", the group said in a statement.
"Globalisation is Alibaba Group's most important strategy for the coming decades, and our goal is to help 10 million global businesses and serve two billion consumers around the world," said Daniel Zhang, Alibaba's chief executive.
Evans "will harness Alibaba Group's leading platforms with direct access to 350 million Chinese consumers to drive increased levels of cross-border commerce between China and the world," the statement added.
Alibaba's Tmall.com site is believed to command more than half the Chinese market for business-to-consumer transactions, while its Taobao platform holds more than 90 percent of the consumer-to-consumer market in China.
But the New York-listed company faces domestic competition from Internet giants Baidu and Tencent, and remains relatively little known outside the country.
Last week it announced it would invest $1 billion (roughly Rs. 6,392 crores) in its cloud computing arm to expand its international presence.
Evans won an Olympic gold medal for his home nation Canada as a member of the men's eights rowing team in the Los Angeles 1984 Summer Olympics.
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