In this study, for the first time, phase and shape controlled copper-based multinary sulfide (M:CuxS, M: Ni, Co, Mn and Zn) nanorods were synthesized using different ratios of dopants. These nanorods were used as the catalyst for the photocatalytic hydrogen evolution, and the effect of the doped metals was investigated under sunlight illumination in the presence of eosin-Y and triethanolamine as a photosensitizer and a sacrificial donor agent, respectively. The reaction rates of hydrogen evolution were found in the order of Ni:CuxS > Co:CuxS > Mn:CuxS > Zn:CuxS as 4.0, 1.2, 0.9 and 0.7 mmol g−1 h−1, respectively. The strategy proposed here is straightforward, holding a great potential to produce high-efficiency catalytic activity and stability of Ni doped CuxS nanorods when compared to the others.