Google announced Diane Greene will run its cloud-computing businesses, including Google for Work, Cloud Platform and Google Apps.
Google created a new position for Greene, who will oversee the previously separate cloud-based businesses.
Greene is an enterprise-technology veteran who co-founded VMware in 1998 and sold it in 2004.
Google wants Greene's experience to help the company win more corporate customers. Google has struggled to attract corporate customers as successfully as Amazon and Microsoft.
"This is an important and fast-growing area for Google and we're investing for the future," said Google CEO Sundar Pichai.
Google currently has an estimated 6% share of the market for cloud infrastructure services, while Amazon's cloud unit is growing at 78% year-over year.
"They very much need to jump-start their cloud efforts," said Crawford Del Prete, chief research officer with International Data Corp.