The order, signed late on Monday, freezes all Venezuelan government assets in the United States and barred transactions with its authorities.
Trump took the step “in light of the continued usurpation of power by Nicolas Maduro and persons affiliated with him, as well as human rights abuses”, according to the order.
The Wall Street Journal said the move was the first against a western hemisphere government in over 30 years, and imposes on Caracas restrictions similar to those faced by North Korea, Iran, Syria and Cuba.
Previous sanctions have targeted Venezuela’s oil industry, the source of most of the country’s export revenue.
The latest order affects “all property and interests in property of the Government of Venezuela that are in the United States, that hereafter come within the United States, or that are or hereafter come within the possession or control of any United States person”.
These assets “are blocked and may not be transferred, paid, exported, withdrawn, or otherwise dealt in”, the order said.
The measure also bars transactions with Venezuelan authorities whose assets are blocked.
It prohibits “the making of any contribution or provision of funds, goods, or services by, to, or for the benefit of any person whose property and interests in property are blocked pursuant to this order,” as well as “the receipt of any contribution or provision of funds, goods, or services from any such person.”
But there are reports that the US will issue “waivers” for remittances and humanitarian aid.
“Venezuela is facing a transnational legal coup planned by the US government,” vice president Delcy Rodriguez said in an interview with local radio station Union Radio.
“They are liars, scammers and thieves … [they want] to strip Venezuela of its assets abroad.”
Venezuelan opposition leader Juan Guaido declared himself interim president earlier this year in a bid to overthrow Maduro, a step that was backed by the US and dozens of other countries.
But Guaido’s efforts have stalled despite the international support and widespread discontent with Maduro, who has been able to cling to power with the backing of the country’s security forces.
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“This embargo will not have a direct effect on the departure of the Maduro government nor will [it] result in a change in the position of the government at the Barbados negotiating table [talks between the government and opposition],” Carlos Pina, a Venezuelan analyst, told Al Jazeera.
“This means that far from inviting Maduro’s government to yield, there will be a situation of increased tension on both sides. The government has shown it has the capacity to cope with external pressures, and specifically with economic sanctions.
“It should also be remembered that Maduro has allies such as China and Russia that could eventually help his government overcome the new sanctions.”
The oil-rich, cash-poor country has been in a deep recession for five years. Shortages of food and medicine are frequent, and public services are progressively failing.
About a quarter of Venezuela’s 30 million-strong population is in need of aid, according to the United Nations, while 3.3 million people have left the country since the start of 2016.
With additional reporting by Elizabeth Melimopoulos