Gaetan Germain's 76th-minute penalty secured a 29-26 win for Brive over European champions Toulon in the Top 14 on Saturday.
The Brive full-back finished with 19 points off the kicking tee, including five penalties, as the Top 14 giants were denied on the road.
Fly-half Willie du Plessis opened Toulon's account within the first minute thanks to a drop goal, but two penalties from Germain put Brive into the lead 6-3 after the first ten minutes.
Penalties dominated the rest of the first half, Pelissié and Du Plessis (twice) striking for Toulon as they finished the ahead at the break 12-9.
Maxime Mermoz's try right after half-time gave Toulon a handsome lead, the conversion from Du Plessis stretching the score to 19-9, before Brive rallied.
The home pack rumbled towards the Toulon line from a driving maul with hooker Guillaume Ribes coming up with the try from the bottom of the pile – Germain's conversion cutting the lead to just three points.
Toulon were then reduced to 14 after multiple penalties, Alexandre Menini taking the punishment, before Germain tied the scores with another penalty at 19-19.
Brive's scrum was now rampant and it created the platform for their second try as Matthieu Ugalde released Teddy Iribaren to score after confirmation from the TMO.
Germain's conversion put Brive ahead 26-19 but Toulon hit back through a try of their own from Lachie Turner, the former Wallaby latching onto Theo Belan's pass to score.
Du Plessis landed the conversion to tie things up before Germain's heroic turn, his fifth penalty from out on the right and 40 metres out sailing through for the win.
Brive as a result leapfrog Toulon into fifth spot, with last season's semi-finalists now in sixth.
Tries: Ribes, Iribaren
Cons: Germain 2
Pens: Germain 5
Tries: Mermoz, Turner
Cons: Du Plessis 2
Pens: Pelissié, Du Plessis 2
Drop Goal: Du Plessis
Yellow Card: Menini
Brive: 15 Gaetan Germain, 14 Alfi Mafi, 13 Arnaud Mignardi, 12 Chris Tuatara-Morrison, 11 Benito Masilevu, 10 Matthieu Ugalde, 9 Teddy Iribaren, 8 Fabien Sanconnie, 7 Dominiko Waqaniburotu, 6 Petrus Hauman, 5 Arnaud Mela, 4 Johan Snyman, 3 Damien Jourdain, 2 Guillaume Ribes, 1 Lucas Pointud
Replacements: 16 Francois Da Ros, 17 Damien Lavergne, 18 Peet Marais, 19 Poutasi Luafutu, 20 Nicolas Bezy, 21 Thomas Laranjeira, 22 Guillaume Namy, 23 Giorgi Jgenti
Toulon: 15 Delon Armitage, 14 Josua Tuisova, 13 Theo Belan, 12 Maxime Mermoz, 11 Lachlan Turner, 10 Willie du Plessis, 9 Jonathan Pelissié, 8 Charles Ollivon, 7 Steffon Armitage, 6 Virgile Bruni, 5 Konstantine Mikautadze, 4 Thibault Lassalle, 3 Mohamed Boughanmi, 2 Anthony Etrillard, 1 Alexandre Menini
Replacements: 16 Bastien Soury, 17 Florian Fresia, 18 Jocelino Suta, 19 Gregory Annetta, 20 Romain Taofifénua, 21 UJ Seuteni, 22 Eric Escande, 23 Thomas Vernet
Referee: Salem Attalah