The Colombia international only moved to Naples a year ago, initially on loan before signing permanently in the summer, but has fallen out of favour under Rafa Benitez.
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West Ham have moved to sign the versatile left-sided player in a bid to bolster a defence that has been decimated by injuries in recent weeks.
Napoli, having themselves secured a deal for Faouzi Ghoulam, confirmed the deal on their official website: “At the same time the SSC Napoli sold Pablo Armero on loan at West Ham until June of this year.”
Partenopei president Aurelio De Laurentiis tweeted: “Good luck Pablo, thanks for your valuable contribution.”
Armero has made 14 Serie A appearances this season, but was omitted from the Napoli squad for their most recent clash against Chievo Verona, while he was part of the side that beat Arsenal 2-0 in the Champions League.
Sam Allardyce has already raided Serie A twice before in the January window, bringing Antonio Nocerino and Marco Borriello to east London from AC Milan and Roma respectively.
Algerian left-back Ghoulam, meanwhile, will replace Armero in the Napoli squad after signing from Saint-Etienne on a four-and-a-half year deal for an undisclosed fee.