Pompeo was addressing the 15-member UN Security Council, which met at his request after Washington and a string of countries in the region recognized Guaido as head of state and urged Venezuelan President Nicolas Maduro to step down.
"Now it is time for every other nation to pick a side. No more delays, no more games. Either you stand with the forces of freedom, or you're in league with Maduro and his mayhem," Pompeo told the council.
"We call on all members of the Security Council to support Venezuela's democratic transition and interim President Guaido's role in it," he said.
Russia unsuccessfully tried to stop the meeting. Moscow opposes the US efforts and has accused Washington of backing a coup attempt, placing Venezuela at the heart of a growing geopolitical duel.
"Venezuela does not represent a threat to peace and security," Russia's UN Ambassador Vassily Nebenzia told the Security Council.
"If anything does represent a threat to peace, it is the shameless and aggressive action of the United States and their allies aimed at the ouster of the legitimately elected President of Venezuela," he said.
Russia, China, South Africa and Equatorial Guinea blocked a US push for a UN Security Council statement expressing full support for Venezuela's National Assembly as the country's "only democratically elected institution."
The same four countries also voted against holding the Security Council meeting. Nine countries voted in favor of the meeting, while Ivory Coast and Indonesia abstained.
Pompeo accused Russia and China of "propping up a failed regime in the hopes of recovering billions of dollars in ill-considered investments and assistance made over the years."
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