Pavey who won a surprise bronze medal in the 5000m at the Commonwealth Games in Glasgow became the oldest woman to win any European championships gold.
The 40-year-old Briton took the lead at the bell lap and held off France's Clemence Calvin to win the race in 32 minutes 22.39 seconds.
"I'm really thrilled. I tried to do a controlled last lap, but when I got to the home straight I thought, just give it all you've got, so you don't regret anything."
Calvin took silver in 32:23.58, while compatriot Laila Traby came third with a new PB of 32:26.03.