The changes come as Alibaba faces headwinds on multiple fronts, including increased competition, a slowing economy and a regulatory crackdown.
The e-commerce giant's Hong Kong-listed shares slid 8% in early morning trade.
Alibaba said it would form two new units to house its main e-commerce businesses - international digital commerce and China digital commerce, in a bid to become more agile and accelerate growth.
The international digital commerce unit will house Alibaba’s overseas consumer-facing and wholesale businesses, and include AliExpress, Alibaba.com and Lazada. The unit will be headed by Jiang Fan, whose past roles include president of the Taobao and Tmall marketplaces.
Alibaba will house its domestic commerce businesses in the China digital commerce unit which be led by Trudy Dai, a founding member of Alibaba, it said.
The company's deputy chief financial officer, Toby Xu, will succeed Maggie Wu as the company's chief financial officer from April, it said, describing his appointment as part of the company's leadership succession plan.
Xu joined Alibaba from PWC three years ago and was appointed deputy CFO in July 2019.
Wu, who helped lead three Alibaba-related company public listings as CFO, will continue to serve as an executive director on Alibaba's board.
Last month the company slashed its forecast for annual revenue growth to its slowest pace since its 2014 stock market debut and saw sales at its banner event, online shopping festival Singles Day, grow at their slowest rate ever.
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