A nanocrystalline tin oxide (SnO2) powders have been prepared by a simple, low-temperature initiated, self-propagating and gas producing by microwave-assisted solution combustion process. The effects of temperature on crystalline phase formation and particle size of nanocrystalline SnO2 and its structure have been investigated. It is observed that heat-treated upto 800°C shows tetragonal phase SnO2. It was observed that the average crystallite size of the annealed SnO2 samples is in the range 9 - 43 nm through controlled heat treatment process. The crystal density of the as-prepared powder is 5.850g cm-3 where as the bulk density is 6.998 g cm−3. The microstructure and morphology were studied by scanning electron microscope (SEM) and HRTEM it is interesting to note that as-prepared SnO2 sample are almost spherical in shape and average agglomerate crystal size of 0.2 – 0.4 μm with increase in calcination temperature, the samples become better morphology than the as-prepared sample. The crystallographic parameters were refined by XRD pattern and Rietveld refinement using TOPAS-3 and Diamond software was used to construct the structural parameters.