Nanocrystalline tin oxides are synthesized via precipitation from heated solutions as well as from a novel abovesolution vapor deposition route that occurs at low temperatures and atmospheric pressure. Crystalline phases are characterized via powder X-ray diffraction. Samples precipitated from reactions of SnCl2 are found to exist primarily as mixtures of tetragonal SnO and tetragonal SnO2 or tetragonal SnO2 and tin(II) oxyhydroxide (Sn6O4(OH)4), depending on reaction conditions. A mixed tin(II)/tin(IV) sample is shown to produce a rarely observed form of the intermediate oxide Sn3O4 upon annealing in air at 600 °C. SnBr2 exclusively forms tetragonal SnO2 via precipitation. Variation in the solvent composition with SnBr2 is shown to result in vapor deposition of SnO2 at temperatures below 160 °C. The average crystallite sizes of the vapor-deposited material are ≈3 nm and grow slowly upon heating. Partially hydrolyzed SnBr4 is proposed as the vapor deposition intermediate based on variations in precursor/solvent combinations along with FTIR and GC-MS analysis of the reaction solution removed prior to the onset of deposition. Synopsis The oxygen stoichiometry of nanocrystalline tin oxide powders is readily varied by controlling reaction conditions when using SnCl2 as the precursor. Mixtures of SnO, SnO2 and Sn6O4(OH)4 are produced and a rarely observed form of Sn3O4 is also generated by annealing a mixed Sn(II)/Sn(IV) sample in air. Substitution of SnBr2 results in exclusive formation of SnO2, either by precipitation or by a novel low-temperature, atmospheric pressure vapor deposition route, depending on reaction conditions.