A series of hierarchical N, S co-doped ZnSnO3/Zn2SnO4 porous hollow octahedrons (NS/ZnSnO3/Zn2SnO4) were constructed using the strategy of combining acid-etching technique with in-situ decoration method for the removal of various pollutants in aqueous environment. The optimized NS/ZnSnO3/Zn2SnO4 exhibited an enhanced photocatalytic activity under simulated sunlight, removing heavy metal ion Cr(VI) in 140 min and rhodamine B (RhB) in 50 min, outperforming hollow Zn2SnO4 and ZnSnO3/Zn2SnO4 octahedrons. This raise could be attributed to the synergetic effect of ZnSnO3/Zn2SnO4 heterojunctions, the introduction of N, S elements and unique hierarchical porous hollow morphology. In addition, the photocatalytic activities of NS/ZnSnO3/Zn2SnO4 for removing Cr(VI) and RhB from mixed pollutant solutions were 1.94 and 1.53-folds as high as those of single system, and it also displayed good reusability and stability in co-existing system, suggesting its potential practical applications in the simultaneous removal of various pollutants from contaminated water.