K2WO4 and K2WS4 were used as precursors for the preparation of alumina, silica and hydroxyapatite supported catalysts whose catalytic performance have been evaluated in the direct reaction of syngas with hydrogen sulfide to produce methyl mercaptan. The solids were characterized using specific surface area measurements, Raman, XRD and X-rays Photoelectrons Spectroscopy, before and after activation (sulfidation). Catalytic performances were correlated to the formation of a KxWS2 phase, evidenced by Raman and XPS, where potassium is assumed to be intercalated in the 1T-WS2 layered phase. Alumina supported catalyst containing high surface concentration of this phase was the most efficient with a CH3SH productivity reaching 72gh(-1) L-1. (C) 2016 Elsevier B.V. All rights reserved.