EU foreign ministers meeting in Brussels announced the measures on Monday 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.
In Monday's statement, ministers said they would focus on security forces, 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.
The EU also stressed that it would not recognize Venezuela's pro-Maduro Constituent Assembly, whose 545 members took office in August and sidelined the opposition-led National Assembly. The EU said its creation has only served to 'further erode democratic and independent institutions.'