Chief Financial Officer Maggie Wu will oversee Alibaba's strategic investments unit, taking over that responsibility from Executive Vice-Chairman Joe Tsai who will support Wu in her expanded role, the firm said on its official WeChat account.
The change comes as Alibaba invests in new business lines such as cloud computing as a boom in its core e-commerce has peaked and revenue growth slows.
Reuters reported last month that the firm is considering raising as much as $20 billion (£16 billion) through a listing in Hong Kong to boost funds available for investment.
"To guarantee innovation, invest in our future, Alibaba is undertaking an organisational upgrade," the company said in a statement signed by Chief Executive Officer Daniel Zhang, who will become chairman when Ma retires on Sept. 10.
The changes are effective from Tuesday, Alibaba said.
Expanding Wu's remit is aimed at more tightly integrating Alibaba's investments into its overall eco-system, said a person with direct knowledge of the matter, who declined to be identified as details of the appointment are not yet public.
Tsai will remain executive vice-chairman, the person said.
Wu has been CFO since 2013. Tsai sits on the board and has served on investment committees of Alibaba Group and affiliate Ant Financial. He joined the company in 1999 and emerged as a key dealmaker, helping draw in investment from the likes of U.S. investment bank Goldman Sachs Group Inc .
Duncan Clark, author of "Alibaba: The House that Jack Built," said Ma's pending resignation made it natural for observers to question Tsai's future at the company.
"Joe is inextricably linked to Jack," says Clark. "As a right hand man of Jack Ma, Ma's imminent retirement begged the question as to whether the right hand man would follow suit."
Tsai declined to comment.
Alibaba's outbound investment has slowed since a flurry of deals in 2014 and 2015, and Clark added the company was increasingly targeting the domestic market.
In its Tuesday statement, Alibaba also said its supermarket division, Freshippo, will become a standalone business, while enterprise software unit DingTalk will be merged into the firm's cloud unit.
(Reporting by Brenda Goh and Josh Horwitz; Editing by Christopher Cushing)
By Josh Horwitz and Brenda Goh