Kent bowlers Darren Stevens and James Tredwell shared nine wickets as Surrey crashed to a 265-run defeat on day three at Canterbury.
Set 370 for victory, Surrey lost Steven Davies in the first over and quickly slipped to 65-5 as Stevens (4-49) ran riot with the new ball.
And there was no way back from there, spinner Tredwell (5-35) taking the final five wickets to fall as Surrey were all out for 104 in 28.2 overs.
Medium pacer Stevens' four-wicket haul gave him career-best match figures of 11-70.
Earlier, Kent skipper Rob Key had completed his 45th first-class hundred as Kent extended their second innings from 167-6 to 230 all out shortly before lunch.
Opening batsman Key carried his bat for 110 not out, his second century of the season, while Surrey seamer Tim Linley (4-48) and spinner Gareth Batty (4-51) each finished with four wickets.
Sixteen wickets fell on day two of Kent's LV= County Championship match with Surrey, with Darren Stevens claiming a career-best spell of 7-21 as the hosts fought back at Canterbury.
With the visitors starting the day on 54-0, Stevens used his swing in a cross wind and thickening cloud while paceman Wahab Riaz also got in on the act as Surrey were dismissed for a paltry 127 inside 44 overs.
Stevens removed Steven Davies (23), Zander de Bruyn (1), Mark Ramprakash (0) and Tom Maynard (16) before mopping up the tail of Yasir Arafat, Tim Linley and Jade Dernbach.
Riaz, meanwhile, had Rory Hamilton-Brown (34) run out and also claimed the scalp of Jason Roy. Surrey's capitulation saw them lose five wickets for 10 runs in the space of 37 deliveries at one point, allowing Kent to secure a surprise first-innings lead of 139.
However, they then lost six wickets of their own during a chilly final session, reaching 167-6 at stumps, with Tim Linley removing Denly, Sam Northeast and Geraint Jones (22).
Stevens, Martin van Jaarsveld and James Tredwell also fell late in the day as a watchful, unbeaten 70 - the only half-century of the match to date - from Kent captain Robert Key held the innings together.
Surrey ended the opening day of their LV= County Championship Division Two clash with Kent on top after bowling the hosts out for 266.
All six bowlers used took wickets before openers Rory Hamilton-Brown and Steve Davies then took 50 runs off the deficit in the last 12 overs of the day.
It was a disappointing return for Kent, whose openers Joe Denly and Rob Key added 80 for the first wicket inside 20 overs as they capitalised on seemingly ideal conditions.
But wickets fell at regular intervals after Zander de Bruyn had Key caught by Mark Ramprakash for 35, Denly the next to fall when he was trapped in front by Tim Linley one short of a half-century.
Sam Northeast (20) became du Bruyn's second victim while Martin van Jaarsveld (13) and Darren Stevens (31) also played themselves in before getting out while the return of new ball bowler Yasir Arafat put the game firmly in Surrey's favour.
He bowled Geraint Jones for a ponderous nine before accounting for James Tredwell and Adam Ball cheaply. Only some late hitting from Matt Coles and Wahab Riaz held up Surrey, the latter making 34 off 44 balls as the pair added 36 for the ninth wicket.
Surrey had 12 overs to see out before stumps, skipper Hamilton-Brown (27) and Davies (23) remaining steadfast.