Police in Bologna said a vehicle accident caused a fire that led to the explosion, and Italian firefighters said a tanker carrying inflammable material was involved.
A lorry carrying cars collided on a bridge with another tanker lorry containing highly flammable propane or butane.
The massive explosion and shock wave were also captured on cell phone video by at least one driver who was stopped to avoid the accident.
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Reuters Firefighters at the scene after the crash caused a huge explosion and fire. The road had been cleared by this point, but still, scores were injured.
At least two people were killed and more than 60 were injured, according to local media.
Video footage and photos uploaded to Twitter show a huge fireball and plumes of smoke rising in the sky in the northern city.
The tanker immediately caught fire, and then exploded a short time later across eight lanes, collapsing part of the raised highway.
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Some people were reportedly hit by flying glass as windows shattered in nearby buildings.
Bologna is the historic capital of the Emilia-Romagna region, in northern Italy.
Police officers told TV news channel Sky TG24 that the extremely high temperatures from the fire and the blast caused the road to collapse.
It took firefighters almost two hours to extinguish the fireball, which spread to vehicles parked in a nearby lot of a auto dealership.
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