Construction of heterostructures with proper band alignment and effective transport and separation of photo generated charges is highly expected for photocatalysis. In this work, Ni-doped SnO2-SnS2 heterostructures (NiSnSO) are simply prepared by thermal oxidation of Ni-doped hierarchical SnS2 microspheres in the air. When applied for the photodegradation of organic contaminants, these NiSnSO exhibit excellent catalytic performance and stability due to the following advantages: (1) Ni doping leads to the enhancement of light harvesting of SnS2 in the visible light regions; (2) the formed heterojunctions promote the transport and separation of photo generated electrons from SnS2 to SnO2; (3) Ni-SnO2 quantum dots facilitate the enrichment of reactants, provide more reactive centers and accelerate product diffusion in the reactive centers; (4) the SnS2 hierarchical microspheres constituted by nanoplates provide abundant active sites, high structural void porosity and accessible inner surface to faciliate the catalytic reactions. As a result, the optimized NiSnSO can photodegrade 92.7% methyl orange within 80 min under the irradiation of simulated sunlight, greatly higher than those of pure SnS2 (29.8%) and Ni-doped SnS2 (52.1%). These results reveal that the combination of heteroatom doping and heterostructure fabrication is a very promising strategy to deliver nanomaterials for effectively photocatalytic applications.