Interior Minister Diosdado Cabello says on Monday that dialogue is not an option.
"With them, there is nothing like that on the table, and with her even less," Cabello said at a press conference.
Delcy Rodríguez took power as interim president after the US military removed President Nicolás Maduro at the beginning of the year.
María Corina Machado is a unifying figure for the opposition in exile and, in addition to negotiations, has called for new elections in the country.
Machado was awarded the Nobel Peace Prize last year for her fight for freedom and democracy. She then gave the physical Nobel Medal to US President Donald Trump.
