The present work studies the effect of zirconium dioxide addition in hydrozincite (Zn5(OH6)(CO3)2). The composites samples shows an efficient photocatalytic activity for H2 production under UV light irradiation and employing methanol as a sacrificial reagent. The composites were synthesized in one-pot method, dried to 100 °C and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), elemental mapping by SEM and transmission electron microscopy (TEM). The most active composite with 3 mol% of ZrO2 exhibited a H2 production of 1908 μmol g−1 h−1 and an apparent quantum yield (AQY) of 41%. The photoactivity is attributed to the formation of heterojunctions, it is confirmed by the characterization techniques. The heterojunctions result in a synergic effect, the hydrozincite provides a wide surface area for electron transfer while the zirconium dioxide inhibits the recombination through the photogenerated holes attraction.