The EU placed Myanmar junta chief Min Aung Hlaing on an assets freeze and visa ban blacklist over a coup and crackdown on demonstrators, the bloc's official journal said.
"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 in Myanmar," the listing said.
Earlier, EU foreign policy chief Josep Borrell said the bloc would impose sanctions on a number of individuals linked to the 1 February coup.
He was speaking as he arrived for a meeting of EU foreign ministers, including Minister for Foreign Affairs Simon Coveney, in Brussels.
While the bloc has an arms embargo on Myanmar, and has targeted some senior military officials since 2018, the measures would be its most significant response so far since the coup.
Stronger measures are expected soon as the EU moves to target the businesses run by the military.
EU diplomats have told Reuters that parts of the military's conglomerates, Myanmar Economic Holdings Limited (MEHL) and Myanmar Economic Corporation (MEC), are likely to be targeted, barring EU investors and banks from doing business with them.
The conglomerates are spread throughout the economy from mining and manufacturing to food and beverages to hotels, telecoms and banking.
They rank among the country's biggest taxpayers and sought partnerships with foreign companies as Myanmar opened up during its democratic liberalisation.
A UN fact-finding mission in 2019 recommended sanctions against the two companies and their subsidiaries,
As the protests continued, motorists honked car horns in Myanmar's biggest city and planted posters in an empty field.
Media reported dawn protests in at least two parts of the commercial hub of Yangon after hundreds of people in Mandalay, including many medical staff in white coats, marched before sunrise yesterday.
The southeast Asian nation has been locked in crisis since the elected government led by Nobel peace laureate Aung San Suu Kyi was overthrown by the military.
At least 250 people have been killed in a harsh crackdown on the protests, according to figures from the Assistance Association for Political Prisoners activist group.
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In the western town of Mindat in Chin state, protesters planted scores of posters in a square in front of the main market saying "Military dictatorship must fail".
Four people were killed and several wounded in the country's second city of Mandalay when security forces opened fire after residents tried to resist efforts by the military to set up a base in a school, the Myanmar Now news portal reported.
The junta says the 8 November election won by Ms Suu Kyi's party was fraudulent, an accusation rejected by the electoral commission.
Military leaders have promised a new election but have not set a date. Western countries have repeatedly condemned the coup and the violence.
Australian media reported that two Australian business consultants were detained as they tried to leave Myanmar, but it was not clear why.
An Australian foreign ministry spokesperson said it was providing consular assistance but declined to comment further for privacy reasons.
Sean Turnell, an Australian economic adviser to Ms Suu Kyi, was detained last month.
The army has not announced any charges against Mr Turnell, who had been advising Ms Suu Kyi on economic policy for several years.
Mr Turnell is among nearly 2,000 people the Assistance Association for Political Prisoners advocacy group says have been detained since the coup.
Meanwhile, a BBC journalist detained in Myanmar on Friday has been released, the broadcaster said.
Mr Aung Thura, a journalist with the BBC's Burmese service, was detained while reporting outside a court in the capital, Naypyidaw.
