This article is concerned with a simple hydrometallurgical method for the selective recovery of germanium from fly ash (FA) generated in an integrated gasification with combined cycle (IGCC) process. The method is based on the leaching of FA with water and a subsequent concentration and selective separation of germanium by a solvent method. Regarding the leaching step, the different operational conditions studied were liquid/solid (L/S) ratio and time of contact. The solvent extraction method was based on germanium complexation with catechol (CAT) in an aqueous solution followed by the extraction of the Ge-CAT complex with an extracting organic reagent diluted in an organic solvent. The main factors examined during the extraction tests were aqueous phase/organic phase (AP/OP) volumetric ratio, aqueous phase pH, amounts of reagents, and time of contact. Germanium extraction yields were higher than 90%. Alkaline and acid stripping of organic extracts were studied obtaining the best results with 1M NaOH (85%). A high-purity germanium solution was obtained. Experimental data presented in this work show that the extraction of germanium by the solvent method designed can be selective toward germanium, and this element can be effectively separated from arsenic, molybdenum, nickel, antimony, vanadium, and zinc.