The move follows Washington slapping punitive sanctions on Caracas after labelling Maduro a "dictator" and as Venezuela scrambles desperately to restructure its debt -- estimated at up to $150 billion -- to stave off default.
Maduro dismisses default possibility on eve of debt talks
The EU said "constructive dialogue and negotiation" were the only way to solve the crisis in Venezuela, where protests against Maduro have turned violent and economic collapse has led to dire shortages of food and medicine.
International powers accuse Maduro of stifling democracy by marginalising the opposition and gagging independent media.
"In addition to its political and diplomatic efforts in support of a peaceful negotiated way out of the political crisis, the council has today decided by unanimity to adopt restrictive measures, underscoring its concerns with the situation in the country," the EU said in a statement.
Venezuela to restructure foreign debt
As well as the arms embargo, the EU has also set up the framework for a blacklist of sanctioned Venezuelan individuals and entities, though for the moment it remains empty.
The EU said it would not recognise Venezuela's Constituent Assembly, the body set up to replace the opposition-dominated congress and which is packed with Maduro loyalists, saying its creation had "further eroded the democratic and independent institutions".
British foreign minister Boris Johnson said the EU wanted to "get Mr Maduro to see sense" through the pressure from sanctions.
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