The British long distance star had never won a major gold medal in an injury-ravaged career stretching back to the 1980s, but outpaced the field in astonishing style to lead home the field.
The mother of two, who turns 41 next month, became the oldest athlete ever to win European gold as she claimed victory in the first track final of the championships.
Pavey, who gave birth to her second child just 10 months ago, clocked a time of 32 minutes 22.39 to lead home French duo Clemence Calvin and Laila Traby by over a second.
"I can't believe it I am just thrilled," the new champion told the BBC.
"I was finding it quite a long way, I thought it was the wrong event at one point! It was really emotional to have my daughter Emily watch me for the first time. We thought she might be scared, but decided to gamble it.
"I was feeling tired, but I had to try and keep relaxed and remind myself that everyone else might be feeling the pace.
"When I got to the home straight I just kept my eyes on the line and concentrated on giving it my all.
"To try for so many years and to finally do it at the age of 40 is funny really. I should have learned how it do it by now."
Jo Pavey of Britain winning the 10,000m title in Zurich
Former marathon star Paula Radcliffe - who is three months younger than Pavey - praised her compatriot's superb tactics.
"It was a really, really smart race from Jo Pavey," Radcliffe told the BBC. "She watched all the moves and saved all her energies until she was ready to make her own attack with a lap to go. It was very canny, very clever."
Germany's David Storl won the other gold medal on offer on the opening day in Zurich as he won the shot put with a throw of 21.41m, beating Borja Vivas and Tomasz Majewski into silver and bronze.
Storl, who has never won a senior title before, was the only man over 21m in the final.
Britain's Tiffany Porter won her semi to make the 100m hurdles final, while Dwain Chambers and James Dasaolu both qualified safely for the men's 100m semi-finals, as did Harry Aikines-Aryeety, and Christine Ohuruogu made it into the women's 400m semi-finals.
Germany's Kai Kazmirek leads the decathlon after day one, and with 4492 points he is 129 points clear of second-placed Andrei Krauchanka.
Wednesday's action sees Mo Farah run in the 10,000m, the British Olympic and World champion once again targeting both 5,000m and 10,000m.
- Sports & Recreation
- gold medal
- Jo Pavey