Photoelectrochemical and photocatalytic hydrogen evolution reaction (HER) have been investigated by using metal free donor-acceptor (D-A) and donor-pi-acceptor (D-pi-A) dyes, which are abbreviated as MC-32 and MC-048, respectively, sensitized TiO2 as a photo-catalyst with or without Cu2WS4 co-catalyst. This co-catalyst is synthesized by a low-cost and simple hot injection method, under visible light illumination. The photoactivities of these dyes have been clarified according to their structural, optical and electrochemical properties. Photocatalytic activities have been slightly increased when added the Cu2WS4 co-catalyst (dye/TiO2/Cu2WS4). This catalytic activity is also compared to that of noble metal Pt (dye/TiO2/Pt). It has been found that 121 mu molg(-1)h(-1), 179 mu molg(-1)h(-1), 348 mu molg(-1)h(-1), 212 mu molg(-1)h(-1), 422 mu molg(-1)h(-1) and 1139 mu molg(-1)h(-1) hydrogen have been evolved by using MC-32/TiO2, MC-32/TiO2/Cu2WS4, MC-32/TiO2/Pt, MC-048/TiO2, MC-048/TiO2/Cu2WS4 and MC-048/TiO2/Pt, respectively. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.