Mr Pashinyan has led weeks of anti-government protests that forced former PM Serzh Sargsyan to resign.
He called for a general strike after ruling party MPs refused to back him as interim prime minister on Tuesday.
Protests broke out across the capital Yerevan and the second city, Gyumri.
Cars and lorries blocked intersections in the capital, while demonstrators stopped traffic on the route to the main airport. Tourists had to abandon vehicles and carry their luggage. Metro stations in Yerevan were closed as part of the campaign of disobedience.
Some of those taking part in the protests in the landlocked former Soviet state of 2.9 million people were school students. The South Caucasus state, a close ally of Russia, shares borders with Turkey and Azerbaijan.
The demonstrators took to the streets after Mr Pashinyan had addressed crowds on Tuesday night in Yerevan's Republic Square, close to parliament, saying that police should also join the protests.
"If everyone participates in a total act of civil disobedience, this will be a total victory of the people of Armenia. Our struggle is a struggle of non-violence, it is a peaceful act of civil disobedience," he said.
Mr Pashinyan fell eight votes short of the 53 he needed to secure a majority in the 105-seat chamber on Tuesday, when he failed to persuade the ruling Republican party to back him.
He warned them during a marathon nine-hour question-and-answer session of what would happen if they rejected his candidacy. "Your behaviour, treating the tolerance of the people as a weakness, could become the cause of a tsunami."
Republican MPs had reportedly given assurances they would not block his bid for office and did not put up their own candidate in a bid to ease tensions. But some MPs accused him of bringing chaos to the streets and questioned whether he was up to the job.
"Mr Pashinyan, I don't see you at the post of prime minister, I don't see you at the post of commander-in-chief," said Eduard Sharmazanov, deputy speaker of parliament and Republican spokesman.
Mr Pashinyan's supporters shouted "shame" when the result of the parliamentary vote was shown on two huge screens in Republic Square.
The opposition leader, accompanied by his wife, arrived in the square soon after, with the crowd chanting "Nikol, Nikol".
***
10:00
Protesters in Armenia on Wednesday blocked some routes into the capital, Yerevan, and a road to the airport, after protest movement leader Nikol Pashinyan announced a nationwide campaign of civil disobedience, REUTERS reported.
The ruling Republican Party thwarted Pashinyan’s bid to take over as prime minister on Tuesday.
“We will be staying here,” David, 19, one of those who blocked the road to the airport, told Reuters.
Protesters also blocked several cross-roads in the city center.
More about: Armenia