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The rational synthesis of semiconducting materials with enhanced photoelectrocatalytic efficiency under visible light illumination is a long-standing issue. ZnO has been systematically explored in this field, as it offers the feasibility to grow a wide range of nanocrystal morphology; however, its wide band gap precludes visible light absorption. We report on a novel method for the controlled growth of semiconductor heterostructures and, in particular, core/sheath ZnO/MoS₂ nanowire arrays and the evaluation of their photoelectrochemical efficiency in oxygen evolution reaction. ZnO nanowire arrays, with a narrow distribution of nanowire diameters, were grown on FTO substrates by chemical bath deposition. Layers of Mo metal at various thicknesses were sputtered on the nanowire surface, and the Mo layers were sulfurized at low temperature, providing in a controlled way few layers of MoS₂, in the range from one to three monolayers. The heterostructures were characterized by electron microscopy (SEM, TEM) and spectroscopy (XPS, Raman, PL). The photoelectrochemical properties of the heterostructures were found to depend on the thickness of the pre-deposited Mo film, exhibiting maximum efficiency for moderate values of Mo film thickness. Long-term stability, in relation to similar heterostructures in the literature, has been observed.