Nanocrystalline tin(IV) sulfide (SnS2) with diverse morphologies were controllably synthesized using organic additives, such as cetyltrimethylammonium bromide (C16TAB), sodium dodecyl sulfate (SDS), p-benzenedicarboxylic acid in ethanol solution under mild reaction conditions. By adjusting the type and concentration of the organic additives, different nanostructured SnS2 were prepared including flower-like, fiber-, layer-rolled and sheet-like forms. Some other factors on the morphology, size and crystallization of the prepared SnS2 nanostructures were also investigated, including reaction time and temperature. Various techniques were applied to characterize the prepared SnS2 nanostructures including X-ray diffraction, Transmission Electron Microscopy and UV–Vis spectroscopy. The trace water or hydration water of SnCl4·5H2O brings no impurities in ethanol solution despite tin(IV) ions are easy to hydrolyze, and the pure-phase SnS2 can be synthesized successfully. Thermogravimetric analysis (TGA) shows that the amount of the passivated additive C16TAB molecule within SnS2 is about 6.4wt.% when the initial molar ratio of C16TAB to Sn4+ is 1:1. This method avoids hydrolyzing and expands the application range of tin salts containing hydration water in synthesizing pure-phase nanocrystalline tin(IV) sulfide.