Boateng joined Milan on a permanent basis in 2011 having initially moved to San Siro on loan from Genoa in 2010 following his transfer from Portsmouth.
The German-born Ghana international scored twice in Wednesday's UEFA Champions League play-off tie against PSV Eindhoven as the Serie A club booked their place in the group stages with a 4-1 aggregate victory.
Schalke have endured a difficult start to the new season, taking just one point from their opening three Bundesliga games, with striker Klaas-Jan Huntelaar sidelined in the 4-0 defeat to Wolfsburg on August 17.
Boateng's arrival will help boost their forward line and the 26-year-old, who has previously enjoyed spells with Hertha Berlin and Borussia Dortmund, was delighted to secure a return to Germany.
"I'm happy to be back home in Germany in the best league in the world," Boateng said.
"The first contact was made a year ago but sometimes you have to wait a bit longer for the good things and opportunities."
Boateng becomes Schalke's sixth signing of the transfer window after left-back Dennis Aogo joined on loan from Hamburg on Thursday.
Manager Jens Keller is confident that Boateng's arrival will have a big impact and revealed that he could feature in Saturday's clash with Bayer Leverkusen.
"He has collected a lot of international experience and I am sure he will help our team greatly," Keller commented.
"He can be used (against Leverkusen), I have an idea of how to use him tomorrow (Saturday)."
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