After Bolivian President Evo Morales blamed the US envoy for inciting protesters in Bolivia - a claim denied by Washington, the US state department declared that the Bolivian ambassador in Washington, Gustavo Guzman, was "persona non grata".
Later on Thursday, Venezuelan President Hugo Chavez said the US Ambassador in Caracas, Patrick Duddy, had 72 hours to leave the country.
Mr Chavez also said he was recalling his envoy from Washington.
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Chavez joins US-Bolivia dispute
Venezuelan leader expels the US envoy in Caracas, in solidarity with Mr Morales.