WASHINGTON—Vice President Mike Pence spoke by phone with Venezuela’s Juan Guaidó and reiterated the U.S. position that Mr. Guaidó is the country’s “only legitimate” leader, a senior administration official said.

The 10-minute phone call on Monday afternoon came after President Nicolás Maduro sought to exert his control over the country on Sunday, with his allies trying to replace Mr. Guaidó as the head of the National Assembly with their preferred choice.

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