ZnS/ZnO heterostructural nanosheets (NSs) are fabricated facilely via a simple solvothermal treatment from ZnS(en) 0.5 (en = ethylenediamine) NSs. The synthesized ZnS/ZnO NSs, with a diameter in the range of 150–350 nm and a thickness of 20 nm, grow on the surface of zinc substrate. Structural characterization revealed that both ZnO and ZnS in ZnS/ZnO NSs heterostructure are hexagonal wurtzite crystal structure. The photocatalytic behavior of ZnS/ZnO NSs is scrutinized using rhodamine B (RhB) as probe molecule under UV light irradiation. The result shows that the photocatalytic activity of ZnS/ZnO NSs is markedly enhanced compared to pure ZnS NSs. Moreover, the reusability test indicated that ZnS/ZnO NSs kept high photocatalytic efficiency after five cycles.