Google is playing catch-up in the booming cloud computing market, well behind the early leader, Amazon. But on Thursday, Google made clear that it was ready to go on the offensive.

The company said that Diane B. Greene, one of its board members, would now head its cloud business that caters to companies. Larry Page, Google’s co-founder and chief executive of the parent company, Alphabet, called her new post a “huge new responsibility at Google.”

The selection of Ms. Greene is sure to make waves in Silicon Valley. The company’s focus and heritage has been mainly on online services for consumers, like search and email, supported by advertising. By placing Ms. Greene, a respected Silicon Valley entrepreneur and technologist, in charge of its corporate business, Google is signaling that it plans to move forcefully beyond its consumer roots.

Ms. Greene is best known as co-founder and former chief executive of VMware, whose software for juggling many computing programs across many computers is widely used in corporate data centers. That kind of “virtual machine” software is one of the technologies that makes computing clouds efficient and relatively inexpensive.