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The Catalan club revealed the 32-year-old has agreed a two-year deal subject to passing a medical.
Simao, who has spent the last 18 months in Turkey with Besiktas, is no stranger to Spanish football. He had a spell with Barcelona earlier in his career, and has also spent three-and-a-half years at Atletico Madrid, with whom he won the Europa League and European Super Cup in 2010.
Espanyol, who begin the new top-flight season at Mallorca on Saturday, have also bolstered their ranks with the signing of Spanish World Cup-winning left-back Joan Capdevila this summer.
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