In chilly and overcast conditions in Portsmouth, Pavey regained the title she won six years ago – only the second 10-mile race of her career.
Her success follows a distinguished track season in which she won European 10,000m silver and finished seventh in both the 5000m and 10,000m at the London Olympics.
Pavey crossed the line in 53:01, just 15 seconds shy of the time she ran six years ago, with Jess Coulson a comfortable second in 53:43 and Berhane Adere holding on for third place in 53:55.
"I wanted to go off at a decent pace and see how my legs feel and keep plugging away," Pavey said.
"I like a flat course and I’m not great at hills, so I knew this course would suit me.
"I need to get more marathon experience, but I so loved focusing on the track this year.
"I’d like to keep going until the next Olympics. Although I’m getting older, it gives me motivation that I can still set a PB this year."
The men’s race was a more tactical affair, but Mokoka - who finished second to Mo Farah in this race three years ago - strode away to take the win in 46:40.
Two-time European cross-country silver medallist Ayam Lamdassem crossed the line four seconds later, just holding off Olympic bronze medallist Tariku Bekele.