Around 500 protesters blocked traffic for several hours on the capital’s main roads to demand justice for two students killed on Wednesday during clashes with police and armed pro-government militias.
When police broke up the crowd on Friday night, the students regrouped at a nearby plaza, where they burned rubbish and threw missiles in clashes which continued through the night.
In a televised address Venezuela’s socialist president Nicolas Maduro said he would not tolerate any more disruptions on the nation’s roads.
He called for calm, but stressed that those who engaged in violence would not go unpunished.
“There will be no coup d’etat in Venezuela, you can be absolutely sure of that, let the whole world know that,” he declared.
However, a number of opposition politicians called for fresh protests.
Caracas mayor Antonio Ledezma said: “Just as we condemn the violent incidents, we say to all Venezuelan families that we have to remain ready to continue fighting, calmly but with determination,”
“You have to know, Maduro, that whatever you do, what started will not stop until change is achieved in peace and with democracy for all Venezuelans.”
There were no reports of serious injuries during Friday’s protests.
The latest unrest followed the burial of the two students. Another victim, a pro-government militia member who was also killed during clashes on Wednesday, was also buried.
It is part of a series of anti-government demonstrations in which protesters have demanded the resignation of Maduro, who succeeded the late Hugo Chavez last year.
Authorities have begun releasing dozens of demonstrators who have been arrested in recent days.
Students in the western states of Tachira and Merida have been at the forefront of the unrest, saying they are fed up with the lack of security and the poor state of Venezuela’s economy.
Venezuela has one of the highest murder rates in the world and is deeply politically polarised, with the opposition blaming the government for the country’s economic troubles.
Venezuela has the highest inflation rate in South America at 56.2 per cent in 2013, according to official figures.