Pompeo sought to counter claims that the chief USA concern is Venezuela's oil, and argued again that Maduro's grip on power was weakening as the country continues to suffer through extended power and water shortages.
Mr Guaido is backed by some 50 countries, while Mr Maduro maintains support from countries such as China, Russia and Cuba.
The US still withdrew dependents of embassy personnel as well as some of the staff, and the secretary of state said the remaining diplomats would be out of Venezuela by the end of the week.
"We detained two people who were trying to disable the power station's communication system at Hury Reservoir", Maduro said in an address streamed live on Periscope.
"When there's no electricity, thank the marvels of modern Cuban-led engineering. When there's no food, thank the Cuban communist overlords".
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Cuba's support comes from a shared ideology, while Russia has "its own reason" for destabilizing Venezuela through spreading disinformation through Russia Today and Sputnik, state-owned news organizations.
On Monday, the U.S. Treasury Department announced new sanctions against a bank jointly owned by Russian and Venezuelan companies for having been "a vehicle for corruption, embezzlement and money laundering [for Venezuelan President Nicolas] Maduro and his cronies".
On January 24 the State Department ordered all non-emergency U.S. government employees to depart Venezuela, where President Nicolas Maduro is facing a stiff challenge for power from opposition leader Juan Guaido amid an acute economic crisis.
Mr Guaido, who heads the opposition-controlled congress, and the United States say Mr Maduro's claims that the USA sabotaged the power grid with a "cyberattack" are an attempt to divert attention from the government's own failings.
US Secretary of State Mike Pompeo meets Foreign Secretary Vijay Gokhale. "And Rosneft's CEO, Igor Sechin, continues to throw a lifeline to the regime", Pompeo said. "The imperialist government of the United States ordered this attack", he said. "There is no ambiguity here about the truth", he said.