The United States on Monday imposed sanctions on a state-owned oil firm in Venezuela, the latest move of the Trump administration to mount pressure on President Nicolas Maduro to cede power to the opposition.
As a lawmaker who also heads the National Assembly, Guaidó has immunity from criminal investigation which can only be removed by a high court.
"If the people in Venezuela want to continue to sell us oil, as long as that money goes into blocked accounts, we'll continue to take it. Be on alert, Venezuela!"
Guaido has been recognized as the nation's rightful leader by two dozen nations that contend the re-election of socialist President Nicolas Maduro was a sham, in part because his strongest opponents were barred from running.
The sanctions on Petroleos de Venezuela, S.A., or PDVSA, will block 7 billion U.S. dollars in assets and could result in a loss of 11 billion dollars in sales next year, U.S. National Security Adviser John Bolton told a White House briefing.
China has said it opposes unilateral sanctions.
"I am the only legitimate president of Venezuela", Guaido told broadcaster ARD.
Several opposition leaders had been forced into exile, jailed or barred from standing in the election, leading the opposition to boycott the poll.
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That followed the United States' decision to hand control of Venezuela's U.S. bank accounts to Guaido, barring Maduro from accessing the funds.
Until now, President Donald Trump had held off on targeting Venezuela's vital oil sector.
In Spain, state-owned shipbuilder Navantia said it has called back four Spanish technicians from Venezuela who were readying for final delivery a navy patrol ship sold 14 years ago to the Venezuelan government.
International Brent crude oil futures rose over 2 percent on Tuesday in reaction. The kind of crude that Venezuela exports, known as heavy-sour, is now scarce due to voluntary cuts in OPEC and Canadian output and the impact of American sanctions on Iran.
Mexico and Iraq are instead most likely to benefit in the race to replace Venezuela heavy crude imported for processing at refineries on the U.S. Gulf Coast, analysts at RBC Capital Markets said in a report.
The Kremlin considers the sanctions against PDVSA as "illegal", a sign of "unfair competition" and an attempt to interfere with Venezuela's internal affairs, Peskov said on Tuesday.
All oil tankers leaving Venezuelan ports would have to pay for crude before departing, he said.
But Venezuela is very reliant on the US for its oil revenue.
"We've seen Venezuelan official and military personnel heeding this call", he added, citing the defection this weekend of the country's military attache to Washington.