Guaido, who declared himself interim president of Venezuela on Jan. 23 with the backing of the United States and most South American nations, said the new board will also oversee PDVSA's U.S. subsidiary, Houston-based refiner Citgo.
"The rescue of our oil industry has begun. CITGO for Venezuelans," tweeted Guaido, who is leading a rejuvenated opposition effort to push socialist President Nicolas Maduro from power. Guaido's representative in Washington, Carlos Vecchio, said that company operations would be maintained as is with the same employees. He said the move was taken to prevent Citgo from being "plundered by the dictatorship."
Officials at Citgo and Venezuela's communications ministry could not immediately be reached for comment. Maduro has previously accused the U.S. and Venezuela's opposition of trying to stage a coup to oust him.
Despite sitting on the world's largest proven petroleum reserves, Venezuela has seen its oil output plummet for years, exacerbating a steep economic collapse. Wresting control of Venezuela's oil industry is a key goal of Guaido as the opposition seeks to remove Maduro, who so far as retained the support of the courts, administration officials and, most importantly, the military.
The Trump administration recently approved sanctions that froze billions of dollars from PDVSA, part of a series of moves aimed at increasing pressure on Maduro to cede power in the oil-rich South American nation.
Guaido said the PDVSA board will be comprised of Simon Antunez, Gustavo Velasquez, Carlos Balza, David Smolansky and Ricardo Prada, while Citgo's board of directors will include Luisa Palacios, Angel Olmeta, Edgar Rincon, Luis Urdaneta, Andres Padilla and Rick Esser.
Venezuela currently pumps just a third of the 3.5 million barrels a day it did when the late Hugo Chavez took office in 1999 and instituted a socialist overhaul of the country. Refining capacity has partly declined following years of poor maintenance and a lack of skilled staff. That has left PDVSA reliant on Citgo to refine the oil and send gasoline back to Venezuela to meet domestic needs.
About 60 countries have recognized Guaido as Venezuela's rightful president. The opposition leader says the constitution allows him to claim the presidency because Maduro's re-election last May was heavily rigged.
About 2 million people have fled Venezuela's hyperinflation and chronic food and medicine shortages in the last two years. Most Venezuelans earn a minimum wage of less than $6 a month, and it is common to see people eating from garbage cans in the streets of Caracas.
On Wednesday, the Netherlands government said it would set up a humanitarian aid hub for crisis-torn Venezuela on its Caribbean island of Curacao. Dutch Foreign Affairs Minister Stef Blok said on Twitter that the collection point would be launched in "close cooperation with Venezuelan interim-president (Juan) Guaido and the United States."
Details weren't released. Curacao is about 55 miles (90 kilometers) off the Venezuelan coast. On Tuesday, Guaido said he was setting a Feb. 23 deadline to bring badly needed food and medicine into Venezuela. The humanitarian aid has been warehoused on the Colombian border since last week. Guaido also announced a second collection point for aid across the border in Brazil.
Maduro is blocking the aid, saying that Venezuelans are not beggars and that the aid is part of the U.S.-led coup.
Associated Press writers Fabiola Sanchez in Caracas and Luis Alonso Lugo in Washington contributed to this report.