The correlations between structural and electrical properties of sprayed SnO2 films have been investigated as a function of substrate temperature (380–560 °C), concentration of tin precursor (0.02–0.8 M SnCl4) and the nature of the doping agent (chlorine, fluorine, antimony). High-resolution transmission electron microscopy has shown that chlorine or fluorine incorporation promotes the same type of defects, which are <0 1 1> twins. These latter behave as neutral defects, the density of which limits the carrier mobility of degenerated fluorine- or chlorine-doped films to around 20 cm2 V−1 s−1. The situation is totally different with antimony. Below the solubility limit in the SnO2 lattice (3%–4% Sb/Sn), Sn4+ are substituted by Sb5+, creating two conduction electrons per site and acting as point-charged defects which lower carrier mobility. Above this limit, the Sb3+ and Sb5+ forms coexist and are associated with an extremely large concentration of structural defects, especially twins induced by the Sb3+ species. These ions enter two-dimensional arrangements on both sides of the twins, making them planar charged defects.