Sylvia Mathews Burwell was named president of the Walmart Foundation, Bentonville, Ark., effective in January 2012, according to a foundation news release.
She succeeds Margaret McKenna, who is retiring.
Ms. Burwell will lead the company's charitable giving efforts and direct Walmart's Global Women's Economic Empowerment Initiative.
The asset size of the foundation was not immediately available.
Ms. Burwell is president of the $37 billion Bill & Melinda Gates Foundation, Seattle. Spokesmen at the Walmart and Gates foundations could not be reached for comment.