Photocatalytic hydrogen production from water in a noble-metal-free system has attracted much attention in recent years. Herein we report on the use of core/shell cadmium sulfide/graphitic carbon nitride (CdS/g-C3N4) heterojunction nanorods modified by nickel hydroxide (Ni(OH)2) as a highly efficient photocatalyst for visible light-driven hydrogen production from water. Due to efficient separation of the photoexcited charge carriers in the CdS/g-C3N4 core/shell nanorods and the synergistic effect of Ni(OH)2, the optimal hydrogen evolution rate over Ni(OH)2-CdS/g-C3N4 is 115.18 μmol h(-1) mg(-1) under visible light irradiation (λ > 420 nm), which is ∼26 times higher than the CdS/g-C3N4 nanorod composite without Ni(OH)2 and ∼7 times better than the 0.5 wt% Pt-CdS/g-C3N4 nanorod composite. The apparent quantum efficiency is ∼16.7% at an excitation of 450 nm. During photocatalysis, no degradation of Ni(OH)2 was observed based on the XPS data, indicating that it is a robust cocatalyst. Moreover, the present photocatalyst showed excellent photocatalytic stability for hydrogen production and the turnover number (TON) reached ∼24,600 over 90 hours.