Tungsten (W)-doped SnO2 is investigated by first-principle calculations, with a view to understand the effect of doping on the lattice structure, thermal stability, conductivity, and optical transparency. Due to the slight difference in ionic radius as well as high thermal and chemical compatibility between the native element and the heterogeneous dopant, the doped system changes a little with different deviations in the lattice constant from Vegard’s law, and good thermal stability is observed as the doping level reaches x = 0.125 in Sn1-x W x O2 compounds. Nevertheless, the large disparities in electron configuration and electronegativity between W and Sn atoms will dramatically modify the electronic structure and charge distribution of W-doped SnO2, leading to a remarkable enhancement of conductivity, electron excitation in the low energy region, and the consequent optical properties, while the visible transparency of Sn1-x W x O2 is still preserved. Particularly, it is found that the optimal photoelectric properties of W-doped SnO2 may be achieved at x = 0.03. These observations are consistent with the experimental results available on the structural, thermal, electronic, and optical properties of Sn1-x W x O2, thus presenting a practical way of tailoring the physical behaviors of SnO2 through the doping technique.