The Finn, 38, was the shock name at the top of the time-sheets ahead of his Ferrari teammate Sebastian Vettel while Lewis Hamilton qualified in third place.
It is Ferrari's first front row lock out at the Italian Grand Prix since 2000 and Raikkonen did it in some style, setting a new fastest lap in the process.
Raikkonen, who is out of contract at the end of the season, said: "The job is only half done. Tomorrow is still another important part."
His lap time of 1:19.119s had an incredible average speed of 164 mph.
Vettel added: "It was unbelievable to see the amount of support around the track.
"I made a mistake on the last run, it was ok but not very good but great to have both cars on front row."
Meanwhile, Hamilton, who was jeered by the Ferrari fans in the grandstands, said: "It was a fantastic qualifying session. Congrats to Kimi.
"We knew they had the pace this weekend and it was going to take something special to catch them.
"It's generally been that gap all weekend. It was amazing how intense it was and that's how racing should be."
Ferrari team boss Maurizio Arrivabene said: "We are not here to remove the smile somebody here, we are here to give the smile to the Tifosi.
"Monza is special and special for Formula One."
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