The blackout disabled traffic lights in the city, causing traffic chaos. It also partially disrupted the underground transport system.
Thousands of workers were sent home. Power was slowly being restored in different areas after the cuts.
Venezuelan President Nicolas Maduro blamed the opposition for "sabotage" to power transmission lines.
"Everything seems to indicate that the far-right has resumed its plan for an electrical strike against the country," he said in a tweet.
But critics say poor management and the failure to invest in infrastructure are to blame.
Authorities say they are working to re-establish services, and they will give priority to transport in Caracas.
The oil industry has not been affected by the power cut, as Venezuela's oil refineries are powered by separate generator plants.
In 2010 the late President Hugo Chavez signed a decree declaring an "electricity emergency" to help his government tackle power shortages.
Although Venezuela has big oil reserves, it is dependent on hydro-electricity for some 70% of its power.
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