TOMS founder and CEO Blake Mycoskie is sitting in a room in New York City’s Mondrian Hotel, schmoozing and talking business with Richard Branson and Arianna Huffington. It’s an informal gathering of members of the “B Team,” Branson’s handpicked group of corporate leaders (which also includes Unilever’s (UL) Paul Polman and Muhammad Yunus of Grameen Bank) who come together every so often to discuss how their companies can be forces for good. Their previous gathering was on Branson’s game reserve in South Africa. (“I hate cities generally, so we normally don’t meet in cities,” Branson says.)
It may sound like a vanity project — corporate titans meeting in private to try to save the world. But that Mycoskie, 37, was tapped to join late last year is significant.
It’s been a big 12 months for the CEO of philanthro-shoe retailer TOMS: He moved back to Los Angeles from Austin after a period characterized by some wrenching soul-searching. He returned to run his company after a nearly two-year hiatus. He opened a manufacturing facility in Haiti. He set up TOMS Marketplace, a benevolent exchange that helps sell other one-for-one products. And he launched a new business, a coffee-bean and retail operation called TOMS Roasting that represents a new direction for the company.
In fact, Mycoskie has had quite a decade. When TOMS launched in 2006, it looked destined to be a fad: cheap, colorful shoes sold in a way that made shoppers feel they’d done some good. But Mycoskie has turned the shoes — and TOMS’ one-for-one model — into a movement, complete with a “One day without shoes” day, a college campus program, and nearly 20 million pairs of shoes donated. “I feel like I’ve been sprinting for a long time,” he says. “It’s been really intense.”
Along the way Mycoskie has become a celebrity to TOMS fans (he has an adoring social media following and is recognized on planes) as well as a savvy marketer, both of the company and himself. Large sheets of paper hang on the wall of his office bearing notes to self, like “storytelling company” and “not too commercial.” He gives TED talks. Comparing himself to Elon Musk, he says, “He got things that God didn’t give me” — meaning where Musk has the scientific genius, Mycoskie sees his strength as being a regular guy who wants to help others.
So far, that’s worked. Now he wants to get the attention of Fortune 500 brands — big companies like P&G (PG) and Bank of America (BAC) — that he hopes will sign on to his new plan to expand into different categories. Mycoskie is betting they will want to partner up on additional products that give back.
For all his ambition, Mycoskie insists he’s no glad-hander: “I appreciate other business owners, but it’s not my peer group.”
If big businesses want to give back, why wouldn’t they choose to do so with Mycoskie? His name, as well as TOMS’, has become synonymous with giving. And his role on the B Team is likely to be the first in a larger ascendancy to come. Mycoskie knows it. “There’s so much runway for us,” he says.
This story is from the April 7, 2014 issue of Fortune.