Jared Borgetti appeared to have sealed Mexico's first ever victory over Italy with a moment of blinding skill in the 34th minute when he glanced an angled header into the top corner of the net from a chipped pass by Cuauhtemoc Blanco.
But five minutes from time, substitute Del Piero headed home from close range to rescue Italy from a dispiriting defeat and put them in the second round although Mexico finished as Group G winners.
The match ended in farce when both teams, knowing the result in the other game with bottom-placed Ecuador beating Croatia 1-0, played keep-ball for the four minutes of injury time.
Italian coach Giovanni Trapattoni said: "Yes, we trembled but we are happy. There was a lot of pressure on us and from the Italian fans.
"We deserved a draw, we created far more chances. There was a good reaction from the whole team after Mexico scored."
Italian midfielder Gianluca Zambrotta added: "It's not easy to come back from a goal down, it's true. But this squad never gives up. We're a great team, a great group of players and when we really get stuck in we know we can carry it through."
Italy had few answers to Mexico's dazzling skills on the ball and rarely threatened Oscar Perez's goal until Del Piero's goal although, for the second game running, they had two "goals" ruled out by a linesman.
Italy finished the group in second place with four points, three behind leaders Mexico. They will play the winners of Group D, South Korea, Portugal or the US.
Ironically, Italy drew 1-1 with Mexico in 1994 to qualify through the group stages before losing to Brazil in the final on penalties. Mexico have never beaten Italy in 10 meetings.
Italy were fighting to avoid the fate of two other pre-tournament favourites, holders France and Argentina, who both crashed out at the first stage of a competition full of upsets.
The Italians started brightly and Filippo Inzaghi had a goal disallowed in the 13th minute after he had been put in by Francesco Totti.
Three minutes later Totti produced a magnificent back-heeled flick into Christian Vieri's path but the burly striker fired high and wide over the bar.
Totti then missed a great chance from 10 metres out, firing wide after Inzaghi had run at the Mexican defence and slipped the ball into his path.
Vieri and Totti then both had good chances to put Italy ahead before Borgetti rose above Paolo Maldini and looped his header over a stationary Gianluigi Buffon in the Italy goal after a stunning build-up for a shock Mexican opener.
The South Americans then built on their goal and continued to play some superb, flowing football for long periods in both halves without any further reward.
Five minutes after the restart Totti put Inzaghi through on goal but the Italy striker hesitated allowing Perez to push the ball away.
Then the Mexicans went close to a second when Jesus Arellano saw a shot cleared off the line by Fabio Cannavaro, after a smart exchange with Blanco.
Trapattoni replaced Inzaghi with Vincenzo Montella as his side desperately sought a goal.
Montella had the ball in the net after another Totti through-ball, but the assistant referee had flagged for offside well before the substitute slotted home.
Once more Totti provided an opening in the 72nd minute with a first-time pass over the top for Vieri but his touch let him down and Perez was able to clear the danger.
It looked as though Italy had run out of inspiration with time running out but then Montella caused panic in the Mexican defence again, clipping over a bouncing cross for Del Piero, a 78th minute substitute, to nod in.
Mexico: Perez; Vidrio, Marquez, Carmona; Morales (Garcia 76), Torrado, Rodriguez (Caballero 76), Luna, Arellano; Borgetti (Palencia 80), Blanco.
Italy: Buffon; Panucci (Coco 63), Cannavaro, Nesta, Maldini; Zambrotta, Tommasi, Zanetti; Totti (Del Piero 78); Inzaghi (Montella 56), Vieri.
Referee: Carlos Simon (Brazil).
Scorers: Borgetti 34; Del Piero 85.
Yellow cards: Arellano, Perez; Cannavaro, Panucci, Totti, Zambrotta, Montella.
HT: 1-0. Attendance: 39,291.
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