Maduro accused Robinson of being a military conspirator against him, wanting to destroy the country's economy and supporting abstention in Sunday's presidential election.
He said he would present evidence of "this conspiracy in the military, political and economic fields," describing Robinson as "an active conspirator who violates international law and abuses it."
"I reject all sanctions against the Bolivarian Republic of Venezuela because it is causing suffering to the Venezuelan people," he said.
Maduro also ordered the expulsion of the second official of the US diplomatic mission, Brian Narango, accusing him of representing the Central Intelligence Agency (CIA) in Caracas.
US President Donald Trump signed a decree limiting Caracas's ability to sell its assets.
There has been no diplomatic representation at ambassadorial level between the two countries since 2010.