Appearing with Newark, N.J., Mayor Cory Booker and New Jersey Gov. Chris Christie, a grinning Zuckerberg announced the creation of the Startup: Education foundation, an initiative aimed at improving education across the country and starting with the previously reported $100 million donation. He said the first project would target Newark, a city in which nearly half of all students don't graduate from high school.
Looking sharp in a blazer and jeans, the famously private 26-year-old CEO offered an unprecedented window into his life, allowing Winfrey's cameras to tape him inside the rented Palo Alto home he shares with his longtime girlfriend Priscilla Chan.
Zuckerberg gave the crew a tour of his modest digs, pointing out his study and kitchen. The cameras also caught Zuckerberg practicing Chinese and pecking Chan on the lips.
Asked by Winfrey why he chose to fund a foundation dedicated to education, he said, "Every child deserves a good education and right now that's not happening."
Oprah: Zuckerberg Initially Wanted to Remain Anonymous
"I've had a lot of opportunities in my life and a lot of that comes from having gone to really good schools. And I want to do what I can to make sure everyone has those opportunities," said the Harvard-educated billionaire, adding that he hopes to "turn Newark into a symbol of educational excellence for the whole nation."
In the lead-up to today's announcement, some in the technology community wondered about the timing of Zuckerberg's $100 million announcement. His "Oprah" appearance comes just one week before the release of "The Social Network," a controversial movie about the founding of Facebook, and two days after Forbes magazine named him the 35th richest American.
Winfrey addressed the timing issue head on, saying "Some people undoubtedly are going to be criticizing the timing of Mark's announcement because we know that there is an unauthorized movie coming out about Mark and Facebook ."
But she emphasized that Zuckerberg's donation had been in the works for months and that it took some cajoling to convince him to appear on her show.
"You're such a shy person and you've been talking about this for months and months and months," she said. "You wanted to remain anonymous and we talked you into coming on here."
Zuckerberg on Facebook Movie: 'A Lot of It Is Fiction'
In a news conference Friday after the show, Booker also stressed that Facebook did not drive the timing of the announcement, and the company initially opposed disclosing the gift so close to the launch of what he called a "fictionalized" movie.
"There was some tense moments when we were talking about the announcement and how to do this. And the governor and I were really pressing to go faster and quicker because he and I have been talking about this issue for a long time," he said. "The movie actually became a complication because Mark's team did not believe it would be good for him to make a public announcement during this time because of the natural cynicism – God forbid, of course, there's no cynicism in the press – the natural cynicism among some that this might be viewed as some elaborate publicity stunt."
Booker said that it was only after long conversations between him, Winfrey and Zuckerberg's team that Zuckerberg decided to discard the anonymous gift option.
"Mark is a 26-year-old young man himself who has a big company that touches the lives of thousands of my residents already. We thought that would be something that would add momentum to what we're doing," he said.
Zuckerberg said the timing of the announcement followed the needs of Newark.
"The thing I was actually most sensitive about with the movie timing was I didn't want the press about 'The Social Network' movie to get conflated with the Newark project, so I was thinking about doing this anonymously just to make sure the two things could be kept separate," he said.
When asked by Winfrey earlier for his take on the movie, which was created without Facebook's participation, he reiterated his view that it's a work of mostly make-believe.
"It's a movie. It's fun. A lot of it is fiction, but even the filmmakers will say that. They're trying to build a good story," he said, adding jokingly, "This is my life so I know it's not that dramatic. … Maybe it would be fun to remember it as partying and all this crazy drama but who knows? Maybe it'll be an interesting story."
In a blog post published to Facebook during the show's taping, Zuckerberg said that education has always been an important issue to him and his family.
"Growing up, my parents emphasized the importance of learning and academic success. They both worked to make sure my three sisters and I could all go to good colleges. My grandmother was a teacher, and when my girlfriend graduated from college she became a teacher as well," he wrote.
Zuckerberg Committed Some of His Facebook Stock to Foundation
During the news conference, he said that the "status quo path" would have been to wait until later in his life to launch philanthropic efforts, but that "after a while of thinking about it decided there's no reason to wait. We should start doing this now."
He said he committed to putting his Facebook stock into the new education foundation, which will then sell off the stock to raise cash. That money will fund the new and improved programs determined by Booker and Christie.
Despite the rare glimpse into his personal life and questions about the movie, Zuckerberg didn't lose focus on his chosen issue of the day: education.
"I started Facebook when I was in college at Harvard," he said. "I have no doubt that if I hadn't had that opportunity then I wouldn't be sitting here today."