The foreign ministry condemned Rousseff's being stripped of office after an impeachment trial in the Brazilian Senate as a "parliamentary coup d'etat."
Venezuela "has decided to definitively withdraw its ambassador in the Federal Republic of Brazil, and to freeze political and diplomatic relations with the government that emerged from this parliamentary coup," it said in a statement.
Rousseff, 68, was convicted by 61 of 81 senators of illegally manipulating the national budget.
The vote ended 13 years of leftist rule in Latin America's biggest economy, depriving Venezuela's socialist leaders of an important ally.
It comes as Venezuela's President Nicolas Maduro finds himself under mounting pressure to submit to a recall election amid a devastating economic crisis.
Ecuador also recalled its top diplomat from Brazil on Wednesday, with leftist President Rafael Correa calling the senate vote against Rousseff "an apology for abuse and treason."
"Never will we condone these practices, which recall the darkest hours of our America," he said on Twitter.
Ecuador's foreign ministry called Rousseff's removal "a flagrant subversion of the democratic order in Brazil."
(This story has not been edited by NDTV staff and is auto-generated from a syndicated feed.)