Virginia's Terry McAuliffe, Colorado's John Hickenlooper, Rhode Island's Gina Raimondo and Louisiana's John Bel Edwards are announcing their support for Perez.
In a statement, Hickenlooper said the two worked together to reform Denver's police department when Perez worked at the Justice Department.
"I can tell you firsthand that Tom's work has made an actual difference in the lives of countless Americans. I've watched him lead large, complex organizations to success, and I know he will do the same at the DNC," Hickenlooper said, calling Perez "an organizer, a progressive, and someone who delivers results."
The backing of four of the nation's 17 Democratic governors gives Perez a counter to the powerful backing his strongest opponent, Rep. Keith Ellison of Minnesota, has already received on Capitol Hill.
Already, Ellison has endorsements from incoming Senate Democratic leader Chuck Schumer of New York and progressive leaders Bernie Sanders and Elizabeth Warren; civil rights icon Rep. John Lewis; Rep. Tulsi Gabbard, a former DNC vice chair; and other lawmakers.
Ellison also locked down the backing of labor unions -- including the AFL-CIO and AFSCME -- before Perez, long a labor ally, entered the race for DNC chair.
Perez, too, has picked up some union endorsements in recent days -- including the United Food and Commercial Workers International Union, the United Farm Workers and the International Association of Fire Fighters.
Ellison has netted support from 15 state Democratic chairs and vice chairs who will vote in the chair race.
Democratic governors, though, have largely stayed on the sidelines in a race that will be decided by the DNC's more than 400 voting members. The only governor to endorse so far is Minnesota's Mark Dayton, who is backing his home-state candidate in Ellison.
Perez said the four governors' support is "indicative of the grassroots focus of my campaign as we continue to work with state and local leaders to unite our party."
"I am thrilled to gain the support from governors representing geographically diverse states that will play a key role in strengthening our party in the years ahead," he said.
Raimondo said Perez "has the determination, management skills and progressive values that speak to the diverse coalition of our party." Edwards said the labor secretary "has a proven track record of winning for the working men and women of this country" -- citing his stances on increasing the minimum wage and equal pay for women.
"He's not only an organizer, but a progressive that gets real results. There's no question that he's the best candidate in the race to protect President Obama's accomplishments and position the party for the future," said McAuliffe, a former DNC chair.
Though the divide isn't even, Perez appears to have stronger support among allies of President Barack Obama and Hillary Clinton, while Ellison is favored by progressives, including Sanders, one of the first to endorse the Minnesota congressman.
Announcing his bid for chair a week ago
, Perez said the DNC has failed to be a "year-round operation" and no longer listens to state-based organizers. He said his DNC would be "very much grassroots" and "bottom up," labeling the recent DNC as too "Washington centric."
"We got our ass kicked in a lot of these rural pockets because we weren't there in sufficient force," Perez said of the 2016 race. "We've got to make sure we don't ignore rural America, because we do it at our peril."
Other contenders in the race for DNC chair are New Hampshire Democratic Party Chair Ray Buckley, South Carolina Chair Jaime Harrison and Idaho Democratic Party Executive Director Sally Boynton Brown.
Ilyse Hogue, the head of NARAL Pro-Choice America, opted Wednesday against running. Ellison has said he'd quit his seat in Congress to focus on running the DNC full-time if he is chosen.