Williams recently served as regional manager for Credit Suisse Private Bank, and was previously a market executive and sales director at Bank of America Private Bank. He also has worked for Morgan Stanley Smith Barney.
"I am excited to be joining Barclays Wealth as it continues its growth and momentum in the Americas and I look forward to the opportunities that lie ahead," said Williams in a statement.
Barclays Wealth has about 250 financial advisors, or investment representatives, in the United States.
"We are extremely pleased to have an executive of Chris's caliber leading the Chicago region," said Mitch Cox, head of Barclays Wealth-Americas and head of global research and investments for all of Barclays Wealth, in a press release.
Barclays Wealth, the wealth-management division of Barclays bank, has 14 offices across the U.S. and Latin America. It has some $230 billion in client assets worldwide.
The group also hired Don Milich and Clifford Wang, both formerly of Morgan Stanley, to work in the firm's Atlanta office several months ago.
Barclays acquired Lehman Brothers' private investment management business in September 2008 and has been using the group as a foundation for building this business in United States and Latin America.
Following the December 2009 merger of BlackRock and Barclays Global lnvestors, including Barclay's market-leading iShares ETF business, Barclays has maintained a 19.9 percent stake in the combined firm.
Jane Wollman Rusoff contributed to this report.