The Spaniard, who had briefly held the leader's pink jersey after winning the 10th stage time trial, was beaten by Chiappucci in the final dash for the line but his second place at the end of the 250km stage over five mountain passes around Corvara Alta Badia was enough to earn him the lead.
Indurain is now poised to repeat his win of a year ago. Understandably, though, Chiappucci was delighted with his stage victory. 'I waited for the right moment. That's all,' he said. 'I could attack again, but I have to admit that Indurain is Superman.'
Chiappucci, second behind Indurain in last year's Tour de France and also runner-up in 1990, mounted the only serious challenge to the Spaniard on a day that saw the eclipse of the other expected challenger, Italy's world champion, Gianni Bugno.
Bugno's energy seemed to fail soon after he refused his rations in the climb up the Marmolada pass, apparently in an attempt to gain time, and he started slipping behind as the temperature dropped to freezing.
His tour hopes had already disappeared after a disastrous performance in Wednesday's time trial, although he still managed a third place in Saturday's 13th stage after breaking from the pack five kilometres from the end.
As usual, Indurain rode effortlessly throughout the stage, never rising from his saddle while others struggled up the steep mountain gradients.
Then, eight kilometres from the finish, Indurain broke away, followed by Ukraine's Vladimir Pulnikov. It seemed the end for Chiappucci, but the Italian found just enough energy to make it first across the line.
TOUR OF ITALY 14th stage (250km, Corvara Alta Badia, It unless stated): 1 C Chiappucci 7hr 27min 34sec; 2 M Indurain (Sp) +1sec; 3 V Pulnikov (Ukr); 4 P Tonkov (Rus); 5 M Lelli all same time; 6 P Ugrumov (Lat) 20. Overall: 1 Indurain 66hr 45min 3 sec; 2 Ugrumov +49sec; 3 Chiappucci +1min 18sec; 4 Lelli +1:38; 5 Pulnikov +2:28; 6 Tonkov +3:08. Selected: 8 S Roche (Irl) +6:39.Reuse content