Surrey clinched the Division Two title after securing two bonus bowling points as Glos closed day one at 385-7.
New Zealander Craig Spearman struck his sixth century of the year, sharing 154 with Phil Weston, dropped at slip on 29, but fell on the stroke of lunch.
Hamish Marshall hit 56 from as many balls with 10 fours and a six, but after Weston fell for 130 Glos faded.
Five wickets fell for 48 but acting captain Alex Gidman hit a watchful unbeaten 21, containing three fours.
Coach Alan Butcher was delighted to capture the title in his first season at the helm:
"I have been extremely pleased with our form in all brands of cricket this year," he said. "It has been a tremendous effort by the guys and I couldn't have asked for anything more."
The Brown Caps are also targeting promotion in the Pro40 League.
They currently lie in third place, which would mean a play-off against the third from bottom team in Division One, which is currently rivals Middlesex.
"To gain promotion in both the four-day and one-day version of the game would be a great result for us and that would have to be the focus now," Butcher added.