The Wales international kicked five penalties to Gareth Steenson's four to seal the win for last season's Heineken Cup semi-finalists.
The match marked Perpignan's return to the second tier of European action after nearly a decade in the Heineken Cup and their experience proved to be vital as they narrowly overcame the Chiefs who are in only their second season of European action.
Fly-half Steenson put Exeter 6-0 up within 10 minutes thanks to two penalties after James Hanks was brought down in the air before Perpignan strayed offside.
Perpignan then conceded another penalty for collapsing the scrum which the Chiefs fly-half slotted to extend the visitors' lead.
However, Exeter were penalised for crossing from the kick-off which allowed Hook, who was making his second start for the club at fly-half, to put the first points on the board for the Top 14 side.
Steenson soon regained Exeter's nine point lead when Perpignan conceded another penalty for pulling back at a line-out.
Hook slotted two more penalties before the break when winger Matt Jess undid the good work of the Exeter scrum when he was penalised for holding on before the Chiefs were penalised for straying offside.
Hook's accuracy left Perpignan trailing 12-9 at the break and the experienced side began to turn the screw early in the second half.
Hook gratefully scored another penalty in the 44th minute when Exeter were penalised at the scrum before Chiefs flanker James Scaysbrook was shown a yellow card for a high tackle on Henry Tuilagi.
Perpignan capitalised on their one-man advantage in the scrum as Exeter were penalised again, with Hook's penalty putting the home side into the lead for the first time in the match.
Steenson attempted a drop goal in a bid to level the scores but the chance floated wide of the right post.
Hook then missed a penalty three minutes from the final whistle but it did not matter as Perpignan held on to take the win.
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