Sylvia Mathews Burwell also will oversee the retail giant’s social, environmental and economic development programs in Africa.

“I feel like this is an exciting time in corporate philanthropy,” said Ms. Burwell, who announced in April that she would be stepping down as president of the Gates Foundation’s global development program. “This offered me the ability to work on problems and challenges at a scale and through the alignment of business and philanthropic interests.”

Ms. Burwell, a native of West Virginia, joined the Gates foundation in 2001 after working in the Clinton administration as deputy director of the Office of Management and Budget, deputy chief of staff to President Bill Clinton and chief of staff to Robert E. Rubin when he was Treasury secretary.

Leslie Dach, Wal-Mart’s vice president for corporate affairs, said Ms. Burwell’s international perspective and experience were particularly attractive to the company. “So much of what we’re trying to do is use our size and scale and business model to make a difference on large social issues, and she can help us with that,” Mr. Dach said.

Wal-Mart’s philanthropy is closely watched in the corporate and nonprofit worlds, as well as by the company’s critics, who dismiss it as an exercise in reputational laundering.

Margaret A. McKenna, who became the company foundation’s president in 2007, put it on the map with major, splashy programs, like its $2 billion commitment to supply food and underwrite improvements in the nation’s food banks. Ms. McKenna’s last day is Friday; Ms. Burwell will start in January.

Last month, the retailer announced it would buy some $20 billion in goods over the next five years from women-owned businesses and put $100 million into training and educating women workers.

The Gates Foundation, the largest in the country with some $36.3 billion in assets, is more willing to work with business than many foundations, joining with pharmaceutical companies on programs to get medicines to needy people in the developing world and with media companies to further education programs. “Even in our financial services, some of our work in Tanzania was done with Vodafone, “ Ms. Burwell said. “But it’s something I’ve just dabbled in and still have a tremendous amount to learn about.”

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