Marissa Mayer, one of Google’s top executives, will be the next CEO of Yahoo, making her one of the most prominent women in Silicon Valley and corporate America.

The appointment of Mayer, who was employee No. 20 at Google and was one of the few public faces of the company, is considered a surprising coup for Yahoo, which has struggled in recent years to attract top-flight talent in its battle with competitors like Google and Facebook.

Mayer, 37, had for years been responsible for the look and feel of Google’s most popular products: the unadorned white search homepage, Gmail, Google News and Google Images. More recently, Mayer, an engineer by training whose first job at Google included computer programming, was put in charge of the company’s location and local services, including Google Maps, overseeing more than 1,000 product managers.

She also sat on Google’s operating committee, part of a small circle of senior executives who had the ear of Google’s co-founders, Larry Page and Sergey Brin.

With her appointment as Yahoo’s president and chief executive, Mayer joins a short list of women in technology to hold the top spot. The elite club includes Meg Whitman, the chief executive of Hewlett-Packard, and Virginia Rometty, the head of IBM. Another senior woman in Silicon Valley, Sheryl Sandberg, is Facebook’s chief operating officer.

For Mayer, Google’s first female engineer, the move to Yahoo is an opportunity to step out on her own and claim a bigger stage. Mayer has been one of the search giant’s most visible and powerful executives, often tapped for keynotes at technology conferences and glamorous magazine spreads. Her life outside of Google, including her posh penthouse in the Four Seasons in San Francisco and her affinity for cupcakes, has been popular Internet fodder.

In a sign of grander ambitions, Mayer, in recent months, had started to find success outside of Google. In April, Wal-Mart, the world’s largest retailer, tapped Mayer to join its board, her first seat at a public company. She is one of four women on Wal-Mart’s 16-person board.

Still, at Google, Mayer did not have a clear path to the C-Suite.

After years of heading its search business, Google’s most profitable unit, Mayer became vice president of the company’s local efforts in late 2010. The following year, Google promoted another executive, Jeff Huber, to be the senior vice president of local and commerce, putting him one level above Mayer. Although Google characterized her move as a promotion at the time, some wondered if she would be content with the reorganization.

An ‘easy decision’

Mayer resigned from Google on Monday afternoon by telephone. She starts at Yahoo on Tuesday. Mayer will also join Yahoo’s board.

In an interview, Mayer said that she “had an amazing time at Google,” where she had worked for 13 years, but that ultimately “it was a reasonably easy decision” to take the Yahoo job. She said Yahoo is “one of the best brands on the Internet.”

She recalled that when she started at Google, the company would conduct user surveys and “people didn’t understand the difference between Yahoo and the Internet.” She said she hoped to focus on creating “really great user experiences” and to attract new talent from Silicon Valley to the company.

“Talent is what drives technology companies,” she said.

Some of Mayer’s mentees at Google include Bret Taylor, Facebook’s chief technology officer, and Brian Rakowski, the vice president in charge of Google Chrome and the product manager who launched Gmail.

Mayer said that as she hashes out Yahoo’s strategy, she is intent on leveraging the company’s strong franchises including email, finance and sports. She also hopes to do more with its video broadband and its mobile businesses.

Still, Mayer is unlikely to try to make Yahoo a direct competitor to Google in the world of search. In 2009, Yahoo gave up its search engine and partnered with Microsoft, which was seen by some analysts as a concession that it couldn’t compete.

“I actually think the partnership has been a positive for the company,” she said.

Mayer said she was first approached in the middle of June about the job after returning from China.

Mayer will be facing an uphill battle as she tries to revive Yahoo. Yahoo remains one of the largest properties on the Web, but it has failed to keep pace with Google and Facebook, which have been more adept at leveraging the increasingly social nature of the Web. In the first quarter, Yahoo’s revenue rose 1 percent from a year ago, after a string of steep declines.

For Yahoo, the hope is that Mayer will provide some much-needed direction for what has been, as of late, a rudderless ship.

In May, Yahoo’s most recent chief executive, Scott Thompson, resigned after questions emerged about whether he lied about certain academic credentials; he had been on the job for only four months. Yahoo’s board of directors has also been reconstituted, adding three members, including Daniel Loeb of Third Point, the company’s second-largest investor, who had been fighting to have Thompson ousted. Michael Wolf, a longtime media consultant and former president and chief operating officer of Viacom’s MTV Networks, was also added to the board.