The design of efficient photocatalysts for hydrogen production by water electrolysis under solar irradiation still remains a challenge. Herein, a series of binary heterojunctions comprising metal sulfides and a zirconium-based MOF were synthesized and employed as photocatalysts for hydrogen production under simulated solar light using different scavengers. The highest hydrogen production rate (64.0 μmol·g−1·h−1) was achieved using the CdS/UiO-66-NH2 heterojunction under cocatalyst-free conditions and using TEOA as a hole scavenger. A synergistic effect between the CdS and the UiO-66-NH2 was confirmed since the single semiconductors exhibited almost negligible hydrogen production. CdS/UiO-66-NH2 characterization revealed that the improved photocatalytic performance was due to the formation of a Type II heterojunction among both semiconductors, thus favouring the separation of photogenerated electron-hole pairs. The findings of this study offer a novel perspective on the development of advanced MOF-based photocatalysts for hydrogen production under solar light.