The meeting with US State Department Counselor Thomas Shannon occurred Wednesday, an agency spokesman said, the same day the advisor met with Venezuelan Foreign Minister Delcy Rodriguez.
"It was a productive exchange and the United States welcomed the opportunity for direct dialogue," spokesman Jeff Rathke said, referring to the talks with Maduro.
He said the US raised "human rights and democracy concerns."
Tensions have run high between the two nations after the US imposed a round of sanctions against Venezuelan leaders.
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Washington and Caracas have toned down their rhetoric in recent days, with Maduro saying he is open to dialogue, and Obama saying Venezuela was not a "threat," despite the sanctions.
Rathke said Caracas invited a Washington official to Venezuela for talks with Maduro on the eve of the Summit of the Americas in Panama attended by Maduro and US President Barack Obama.
The US is "open to direct engagement" with Venezuelan officials, Rathke said.