Among those targeted was junta chief Min Aung Hlaing, who was hit with an assets freeze and travel ban, and Deputy-Commander-in-Chief, Soe Win.
The move followed a meeting of EU foreign ministers in Brussels.
"Commander-in-Chief Min Aung Hlaing has been directly involved in and responsible for decision-making concerning state functions and is therefore responsible for undermining democracy and the rule of law," the EU’s official journal said.
EU 🇪🇺 sanctions 11 people over the military coup and ensuing repression in 🇲🇲 Myanmar/Burma
— EU Council Press (@EUCouncilPress) March 22, 2021
👉 https://t.co/wLzuSNkSRY
AND 11 people & 4 entities responsible for serious #humanrights violations in China, DPRK, Libya, Russia, South Sudan and Eritrea
👉 https://t.co/Tg3X56YjcE pic.twitter.com/RTihe06WYY
At least 250 people have been killed in protests against the military junta. Monday’s sanctions are the EU’s strongest response so far.
Speaking to reporters in Brussels, German Foreign Minister Heiko Maas said the number of "murders" in Myanmar had reached an “unbearable” level, and the EU could not avoid imposing sanctions.
"We don't intend to punish the people of Myanmar but those who blatantly violate human rights," he said.
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France repeats calls to end violence against protesters in Myanmar
In a statement, the EU said it would continue to review all of its policy options, including “additional restrictive measures against economic entities owned or controlled by the military”.
Myanmar’s military junta claims elections last November – won in a landslide by Aung San Suu Kyi’s party – were tainted by fraud, and its troops have prevented the parliament from convening.
Internet access in the country has been severely restricted amid a widespread clampdown on the media and politicians.