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Napoli have settled a £31.8 million offer with Madrid for Higuain, with the Argentina international signing a five-year, £140,000-per-week deal.
Rafael Benitez, who was appointed as Napoli's new boss in May, targeted Higuain for the vacant striker role which was vacated by Edinson Cavani, who moved to Paris Saint-Germain for £55m earlier in July.
Napoli have already purchased two players from Madrid this summer, with defender Raul Albiol and attacker Jose Maria Callejon moving to Serie A, while Dries Mertens, Pablo Armero, Josip Radosevic, Rafael and Emanuele Calaio have also joined Benitez's side.
Liverpool goalkeeper Pepe Reina also completed a loan move to Napoli earlier this week.