The effect of tungsten carbide as co-catalyst in the photocatalytic H-2 production from ethanol aqueous solutions (25% v/v) is reported. The photocatalytic H-2 production using WC/TiO2 systems, in which tungsten carbide NPs are dispersed onto TiO2, is compared with that of TiO2 800 with morphological and structural characteristics similar to WC/TiO2 and with the hydrogen produced using commercial TiO2 P25 as reference. To this end, WxCy/TiO2, WC1-x/TiO2 _US and WO3/TiO2 photocatalysts were prepared, characterized and tested. The preparation of WxCy/TiO2 was accomplished by using a sol-gel based method which was useful for preparing bulk tungsten carbides. The preparation of WC1-x/TiO2 _US is reported by the first time using a sonication method from WC1-x and TiO(2)800. Materials were characterized using N-2 physisorption, XRD, SEM-EDX, TEM-HRTEM, UV-vis RDS, XP and Raman spectroscopy. The presence of 2-3 nm NPs with different tungsten carbide crystalline phases (hexagonal WC and W2C and cubic WC1-x) was determined for WxCy/TiO2 photocatalyst, the solely presence of 2-5 nm cubic WC1-x NPs onto TiO2 was confirmed for WC1-x/TiO2 _US. The presence of tungsten carbide NPs onto TiO2 improves the photocatalytic behavior of TiO2 in terms of hydrogen production. The effect of tungsten carbide NPs in the C2-C4 products derived from ethanol is discussed and the reusability of the photocatalyst is also studied. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.