EU foreign ministers meeting in Brussels announced the measures in response to regional elections last month, which they say worsened the country's crisis.
The weapons ban is intended to prevent the government of President Nicolas Maduro from purchasing military equipment that could be used for repression or surveillance.
The sanctions also include setting up a system for asset freezes and travel restriction on some past and present Venezuelan officials close to Maduro.
Spain has long pushed for sanctions on those close to Maduro, but the EU has been divided over whom to target.
Ministers, however, said in Monday's statement that they would focus on security forces and government ministers and institutions accused of human rights violations, and the disrespect of democratic principles or the rule of law.
Last Thursday, the U.S. imposed financial sanctions on 10 current and former Venezuelan officials because of corruption and abuse of power allegations related to Maduro's crackdown on the opposition.