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At almost the exact moment Michelle Rhee took to a podium at a downtown D.C. hotel ballroom to announce her departure as the District’s schools chancellor in October, people working for her flipped the switch on a fancy new website, Facebook page, and Twitter account.

The well-choreographed roll-out was followed the next day with Rhee making the rounds on the network morning shows, marking the beginning of a media cycle that’s showed no sign of slowing since. Less than two months after her resignation, Rhee was sitting on Oprah’s comfy chairs announcing plans for a new advocacy group, StudentsFirst, that has already become a dominant force at the nexus between education and politics.

Just how was Rhee able to cement her brand as a national player so quickly? After all, there were reports from the Wilson Building that as of the morning after Adrian Fenty’s primary defeat, Rhee was still interested in staying on as chancellor. That, of course, wasn’t meant to be. She had become famous in three years at the D.C. Public Schools; as she shifted into the private sector, it became clear that she also had a ready-made organization standing by to keep her in the spotlight.

Most of the people who helped build and launch Rhee’s group, and the ones running it now, already had impressive national résumés—which shows the power of the political brand she built in D.C. They include: Anita Dunn, the former White House communications director, who helped Rhee get StudentsFirst up and running and who advised Rhee at DCPS through an outside contract; Tali Stein, a fundraiser for Hillary Clinton’s 2008 presidential bid, who is now vice president of development for StudentsFirst; Joe Rospars of Blue States Digital, which built Rhee’s site and did the same for Barack Obama’s campaign in 2008; Hari Sevugan, former Democratic National Committee spokesman, now running StudentsFirst’s communications shop; and Bradley Tusk, who ran New York City Mayor Michael Bloomberg’s 2009 re-election campaign and is now StudentsFirst’s political consultant.

(StudentsFirst has also been a home for a few former staffers of Rhee’s old political patron. Fenty’s spokeswoman Mafara Hobson works for StudentsFirst, as does his failed pick to lead the parks department, Ximena Hartsock, who was rejected by the D.C. Council and later found by the inspector general to have lied on a federal form and improperly hired a friend.)

The narrative Rhee and her advisers are pushing is pretty simple: StudentsFirst’s popularity is due in part to frustration with the sorry state of many of this country’s schools and the chokehold many teachers’ unions have on policy discussions.

“The reality is there are people who care a great deal about education reform in this country, there are people who want to find out how they can do more, there are people who want to know what they can do in their own communities, or who want to seek out someone who can give them advice,” Dunn told me shortly after StudentsFirst debuted.

Being the heroine of the critically acclaimed documentary Waiting for “Superman” didn’t hurt Rhee, either.

But there are two other, more important reasons why Rhee and StudentsFirst have gotten so big so fast: Rhee is a great fundraiser, and really rich people love giving money to education causes. (Think Facebook founder Mark Zuckerberg’s $100 million gift to Newark, N.J.’s public schools, just as an unflattering biopic came out.) Getting her new organization off the ground was only a matter of asking the same people she’d been asking for money for years to give it to a different place.

Rhee’s long-time deputy and successor in D.C., Kaya Henderson, has seen Rhee’s fundraising prowess up close many times. Henderson says Rhee’s brash and “ballsy” public persona is exactly the same when she’s behind closed doors with billionaires who can write checks with six or seven zeros at the end.

“She is bold. I think really there are a lot of people who are measured and not willing to go out as far as she is,” says Henderson. “I’ve seen her shake her booty and get some cash over and over again. She’s a very good fundraiser.”

Henderson recalls one instance when Rhee told one wealthy philanthropist (Henderson wouldn’t say who, except “it was not a small person”) that he was wasting his money and “if he really wanted to help education, he’d shut his foundation down.”

Billionaire Eli Broad told New York magazine that StudentsFirst planned to raise $50 million for start-up costs from 20 individuals and eventually spend $200 million a year. Those are jawdropping numbers at first blush, but not much of a stretch for Rhee when you consider her background.

That’s because a fair amount of Rhee’s time in D.C. was spent hitting up big-dollar philanthropists to help raise more than $60 million in private funds to help pay for a new contract that emphasized merit pay and de-emphasized seniority. Rhee’s calendar as chancellor shows she was in regular contact with the bigwigs of the education philanthropy machine, including the charitable arm of the Wal-Mart fortune and Bill Gates’ and Broad’s foundations.

Henderson says Rhee’s ability to get that contract approved is probably one of the biggest reasons why wealthy donors have been willing to open their wallets for Rhee’s new gig.

“It brought a renewed sense of possibility for rich people for what their money could actually leverage,” says Henderson. “For a relatively small investment, they got a very radical teachers’ contract.”

That same equation may be at play with Rhee’s new outfit. After all, even rich people can’t resist a bargain.