The couple owned a pizza and pastry shop, Da Frank, on via Saviore, which was a popular meeting point for young people in the city.
The shooting happened on the street outside the shop at around 10am, with the attackers reportedly fleeing on a scooter.
The woman died instantly while her husband and owner of the business, Francesco Serremondi, is fighting for his life in hospital, Corriere reported.
A 43-year-old staff member was also injured after being shot just metres away from the shop a few months ago, the newspaper said.
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