Prime Minister Miloš Vučević said "this is a black Friday for us, for all of Serbia," as the government declared Saturday a national day of mourning.
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A vigil has taken place in northern Serbia for those killed when the concrete roof above the entrance of a railway station collapsed as the death toll rises to 14.
The general manager of the Novi Sad hospital said at least three people were in a critical condition, with two undergoing surgery for "life-threatening" injuries.
Interior Minister Ivica Dačić said he feared the death toll would rise as rescue teams continue to clear away the rubble with heavy machinery.
"This is one big, it's one huge accident. Unfortunately, despite all of us being ready to react, police, firemen, rescuers, ambulances, the medical workers had nothing to do simply because there were more dead than those injured," he said.
In a television address from the capital Belgrade, President Aleksandar Vučić expressed his condolences to the families of the victims.
"A great thank you to all good people in Serbia who donated blood, who came to help in the rescue of the injured and killed and I believe that we will be able to learn a lesson from this hard day," he said.
Serbia's state railway company, Železnice Srbije, said the accident happened at 11:50 am.
The company said the construction above the station entrance was not part of recent reconstruction work which had taken place on the station building.
The station has reportedly been renovated twice in recent years.
Prime Minister Miloš Vučević said "this is a black Friday for us, for all of Serbia."
Vučević said the roof was built in 1964 and an investigation was under way to determine what happened and who was responsible for the tragedy.
In response to appeals for his resignation, Infrastructure Minister Goran Vesić also said that the building permit for the reconstruction did not include the external awning.
However, Serbian experts told domestic media that the renovation work might have caused a structural change to the building, indirectly resulting in the roof's collapse.
Serbia's government has declared Saturday a day of mourning.
"If one roof top could not be built properly, then I don’t know what to say. It was renovated three months ago. I don’t know what to think. I am a student and I use that train station. I go to Belgrade to visit friends. What can I say, it's a catastrophe," said Novi Sad local, Ivan Trifunović.