Maxi died early on Friday morning, the district authority for Berlin-Mitte confirmed. She was known to have been seriously ill, although the exact cause of death is not known. There will now be an investigation into how she died.
The two female brown bears Maxi and Schnute have been the centre of a debate between the city and animal rights activists for years. Critics have said that the bears, kept in a 460-square-metre compound in a park near the Spree River, do not have enough space.
The compound opened in 1939 and has housed bears regularly, as symbolic guardians of the city. After Maxi and Schnute, no further animals will live there.
Animal rights campaigners are calling for 32-year-old Schnute, Maxi's mother, to be removed from the compound as soon as possible.
It remains unclear whether she will stay, or find a new home somewhere else to live out the rest of her life with a little more space.