Puig's fellow countryman, Alex Criville made the crowd's day complete when he won a thrilling battle for third place with Japan's Norifume Abe, riding a Yamaha.
Doohan had seemed to have the race in his pocket, going well clear until a dramatic loss of control on lap 21 sent him hurtling into the gravel and out of contention. The slip cost him the lead in the world championship standings, his fellow Australian, Daryl Beattie taking over at the top after finishing seventh.
Puig realised once he had inherited the lead that he simply had to maintain his concentration to take what might prove his best chance to win at home.
Doohan, bidding for his third win in four races this season, made a relatively slow start on his Honda, with Cadalora setting the pace, but he had moved smoothly through into the lead by the fifth lap and increased his advantage until his spectacular exit.
The most painful mishap of the race was a ninth lap spill by the Italian Loris Reggiani, whose Aprilia slid off on a tight bend: he broke his left hand and right foot.
SPANISH GRAND PRIX 500cc (27 laps, 119.421 km): 1 A Puig (Sp) Honda 47min 45.728sec (ave speed 150.020 kph); 2 L Cadalora (It) Yamaha 47:50.821; 3 A Criville (Sp) Honda 47:59.759; 4 N Abe (Japan) Yamaha 47:59.992; 5 A Barros (Bra) Honda 48:07.869. World championship standings: 1 D Beattie (Aus) Suzuki 74pts; 2 M Doohan (Aus) 70; 3 Puig 56; 4 Criville 48; 5 Cadalora 46.
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