It's not clear whether Prince, who has been accused of back-channeling on behalf of the Trump administration before and whose sister is Education Secretary Betsy DeVos, was carrying a message from the White House, which has imposed severe sanctions on Venezuela barring Americans from doing business with President Nicolas Maduro's socialist government.
Prince traveled to Caracas for the late November meeting with Vice President Delcy Rodriguez after alerting U.S. officials, said one person briefed on the meeting. Rodriguez, a staunch Maduro ally, is one of several dozen Venezuela officials sanctioned by the U.S.
At a private dinner at Rodriguez's home, Prince is believed to have urged the release of six employees of Houston-based Citgo, said the person, who spoke on the condition of anonymity because of the sensitive nature of the visit.
Two weeks later, the six men — five of them dual U.S.-Venezuelan citizens — were granted house arrest. They have been held for more than two years on charges of embezzlement.
Two other people also said they were aware of the meeting but had fewer details of what was discussed. A third person said Prince's visit had nothing to do with the Citgo case.
Rodriguez did not reply to a request seeking comment nor did her brother, Communications Minister Jorge Rodriguez.
Marc Cohen, a spokesman, said Prince had no comment.
The trip marks something of a reversal for Prince, who earlier in the year had been pitching a plan to topple Maduro, and it raises questions about whether U.S. insistence on regime change in Venezuela has shifted.
Elliott Abrams, the U.S. special envoy to Venezuela, said Prince didn't represent the U.S. government in the meeting. He also said there is no change in U.S. policy opposing Maduro remaining Venezuela's president.
"Neither the meeting nor any offers made were on behalf of the United States Government, and on their face such offers would appear to violate U.S. sanctions," Abrams said.
He also reiterated U.S. backing for opposition leader Juan Guaido, the head of Venezuela's opposition-controlled congress who is recognized by the U.S. as Venezuela's rightful president.
"The United States fully supports Juan Guaido and looks forward to his re-election as president of the National Assembly. He is the leader of the opposition and the symbol of democratic change for Venezuelans; he personifies their struggle to restore democracy to their country," Abrams said.
Prince, a major Republican donor, has been accused of acting as a back channel on behalf of Trump before. As Trump was preparing to take office in 2017, Prince met with a official close to Russian President Vladimir Putin in the Seychelles, islands off the coast of east Africa. Special counsel Robert Mueller's report on his Russia investigation said the meeting was set up ahead of time with the knowledge of former White House aide Stephen Bannon.
Prince soared to notoriety after Blackwater employees in 2007 shot and killed Iraqi civilians in Baghdad's Nisour Square during the Iraq war, casting a light on the role played by private contractors in U.S. military operations overseas.
In the wake of the scandal the company's name was changed and Prince sold his shares to a private equity fund. Today the former Navy SEAL heads a private equity fund focused on investments in frontier emerging markets.