Photoelectrochemical and photocatalytic hydrogen evolution reaction (HER) have been investigated by using metal free donor-acceptor (D-A) and donor-π-acceptor (D-π-A) dyes, which are abbreviated as MC-32 and MC-048, respectively, sensitized TiO2 as a photocatalyst 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 μmolg−1h−1, 179 μmolg−1h−1, 348 μmolg−1h−1, 212 μmolg−1h−1, 422 μmolg−1h−1 and 1139 μmolg−1h−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.