Brive overpowered Scarlets in a bruising Amlin Challenge Cup quarter-final to set-up an all French last four showdown with Biarritz Olympique.
Riaan Swanepoel's five penalties guided the 1997 Heineken Cup winners past the Welsh region in an error-strewn clash.
Liam Williams finished a flowing move for the Scarlets in the second-half, the full-back stretching out after Andy Fenby's offload to score the only try.
Stephen Jones converted two penalties but Scarlets rued three missed kicks.
Experienced fly-half Jones missed two early penalties before Priestland failed to land a conversion on the left touch-line after Williams's sixth try of the season.
But Brive won the battle of the breakdown as the Llanelli side were eliminated from a European tournament by a French side for the fifth time in 15 years.
And Brive completed a quartet of French Top 14 teams in the Amlin Cup semi-finals as they will face Biarritz Olympique at Parc des Sports Aguillera on Saturday, 28 April while Toulon will play Stade Francais the day before.
Moments after Wales international Jones fired a fifth-minute penalty wide, Swanepoel moved Brive into the lead from a penalty following a Scarlets offence at a scrum on the edge of their 22.
The South African could have doubled the lead but he nudged a penalty wide of the left post before Jones missed straight-forward effort in front of the posts 25m out.
The British and Irish Lions fly-half made amends moments later after England number eight Ben Morgan powered forward and referee Wayne Barnes penalised Brive for failing to roll away.
Swanepoel smashed the French side ahead with a penalty just a couple of metres inside the Scarlets half before Jones responded with a tough but successful kick from wide on the right as a tight, physical first-half ended level.
Two more pin-point Swanepoel kicks early in the second-half put Brive in control as the home forwards took control of the scrum.
Scarlets were given hope when Brive fly-half Shane Geraghty was sin-binned a shoulder charge on Fenby - and five minutes later the Scarlets wing tipped Rhys Priestland's pass into Williams' path and the Wales squad player made the line.
He just about held off Mathias Atayi and Ronnie Cooke to barge over for a score that needed the approval of TMO Graham Hughes.
The visitors' try inspired Brive into life and Poutasi Luafutu came within inches of scoring following Fenby's attempt to keep Priestland's 22m drop-out in play.
Sevania Galala robbed the Scarlets wing and smashed towards the line. He fed Davit Khinchagishvili and the prop found Luafutu, but some resolute defence kept the Kiwi flanker out.
However, Swanepoel's fifth successful kick, in the last minute, ensured a Brive quarter-final triumph, just like in the two team's first meeting in the 1997 when the French side progressed to win that year's Heineken Cup.
Brive: M Atayi (S Spedding 62); J Boussuge, R Cooke, R Swanepoel, S Galala; S Geraghty (A Mignardi 72), J Pejoine (A Figuerola 62); J Poirot (D Khinchagishvili 54), V Lacombe (c) (I Natriashvili 54), P Barnard (A Barozzi 54), J Le Devedec (R Uys 71), O Caisso, V Forgues (P Luafutu 56), A Bias, P Hauman
Scarlets: L Williams; G North, G Maule (S Lamont 61), J Davies, A Fenby; S Jones (R Priestland 50), G Davies (R Williams 80); R Jones (P John 71), M Rees (K Owens 50), P Edwards (S Gardiner 56), S Timani, D Welch (K Murphy 66), J Turnbull, J Edwards (M Gilbert 71), B Morgan.
Referee: Wayne Barnes (RFU)