Large crowds of flag-waving protesters clogged the downtown area of the capital on Saturday, with people hardly able to move and many stuck hundreds of metres away from the planned protest venue.
Following apparent sporadic incidents between protesters and the police, university students — who have been leading the peaceful protests for the past four months — abruptly called for an end to the demonstration, saying they no longer can guarantee safety at the rally.
Most of the protesters dispersed, but thousands remained on the streets as tensions surged.
Police said the crowd reached 107,000 people at the peak and independent media described the rally as the biggest ever in the country, saying the numbers were much higher.
All public transport in Belgrade was cancelled as protesters streamed into the city from various directions.
The rally was part of a nationwide anti-corruption movement that erupted after a concrete canopy collapsed at a train station in Serbia's north in November, killing 15 people.
Almost daily demonstrations that started in response to the tragedy have shaken Vucic's firm grip on power in Serbia like never before in the past 13 years in charge. Many in Serbia blamed the crash on rampant government corruption, negligence and disrespect of construction safety regulations, demanding accountability for the victims.
Saturday's rally was dubbed "15 for 15," referring to the date of the protest and the number of people killed in the city of Novi Sad on November 1. The crowd fell silent for 15 minutes in the evening to honour the victims.
Ahead of the demonstration, Vucic repeatedly warned of alleged plans for unrest while threatening arrests and harsh sentences for any incidents.
A deafening sound of whistles, drums and vuvuzelas filled the air and some protesters carried banners that read, "He's Finished!" Crowds chanted "Pump it Up", a slogan adopted during past four months of student-led protests.
Protesting university students have been a key force of the anti-graft movement with their call for justice.
Students' determination has struck a chord among the citizens who are disillusioned with politicians and have lost faith in the state institutions.