Interior Minister Ivica Dacic said that three people were rescued and hospitalised with serious injuries, and that he did not expect the death toll to rise much further.
“When we had eight victims, we knew that there were five more people under the rubble for whom we could not establish whether they were alive or dead,” Dacic told reporters.
He said they did not show any signs of life.
“Death occurred on the spot,” Dacic added.
Ambulances and other emergency teams were dispatched to the downtown station and bulldozers were removing the debris looking for survivors.
Some 80 rescuers were at the scene as heavy machinery removed large parts of the rubble.
Surveillance camera footage showed people moving in and out of the building and sitting on benches on a bright, sunny day before the concrete canopy suddenly collapsed.
The building was recently renovated.
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Dacic said the rescue operation was “extremely hard” and that it would last for several more hours.
Serbia’s government declared 2 November a day of mourning.
Residents of Novi Sad were lighting candles across the street from the railway station in an expression of grief for the lost lives.
Prime Minister Milos Vucevic said, “This is a black Friday for us, for all of Serbia.”
Vucevic said the roof was built in 1964 and an investigation was underway to determine what happened and who is responsible for the tragedy.
The renovated station was inaugurated by Serbian President Aleksandar Vucic and his populist ally, Hungarian Prime Minister Viktor Orbán, over two years ago as a major stopover for the planned fast train line between Belgrade and Budapest.
Serbia’s state railway company said the accident happened at 11.50am local time.
The company said the structure above the station entrance was not touched during the recent renovation.