McLaren's Lewis Hamilton finished fourth after a thrilling battle with the old master Michael Schumacher, a five-times winner at Monza in his glory days with Ferrari, and then striving in vain to catch Alonso over the closing laps.
Schumacher gave no quarter, his defensive driving prompting a frustrated Hamilton to question whether the seven-times champion's moves were legal.
That triggered a veiled warning from Mercedes team boss Ross Brawn to Schumacher, reminding him to leave enough space at the Ascari chicane.
While Hamilton and Schumacher tussled, Button caught them both napping and passed in quick succession.
"I don't know if we could have challenged Sebastian today... it's a pity we had such a poor start," said Button, who qualified third but was sixth at the end of the first lap.
Schumacher, with plenty of fans in the throng of flag-waving tifosi flooding onto the finish straight for the podium celebrations, finished fifth ahead of former Ferrari team mate Felipe Massa.
Massa was the last unlapped driver on a day when only 15 of the 24 starters finished at the fastest circuit on the calendar.
Spain's Jaime Alguersuari was seventh for Toro Rosso and Britain's Paul di Resta, of Italian descent, eighth for Force India.
Brazilian Bruno Senna, nephew of the late triple champion Ayrton, scored his first points in Formula One with ninth place for Renault and Swiss driver Sebastien Buemi claimed the final point for Toro Rosso.
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