Antimony-doped tin dioxide(ATO) nanoparticles with primary diameter in the range of 9-10 nm were rapidly synthesized via a novel combustion technique, starting with antimony trichloride and tin tetrachloride as metal sources and self-assembly compounds as fuels. The combustion phenomena and characteristics of products were controlled by assembling components in fuel compounds according to appropriate molar ratio. The as-synthesized products were characterized by XRD, SEM, TEM and XPS, respectively. The electrical conductivity was evaluated through measuring the antistatic property of polyester fiber treated by the as-synthesized products. The results show that a mild combustion phenomena without release of smoke can be taken on and perfect azury rutile ATO crystal with complete substitution can be formed rapidly under the appropriate synthetic conditions. The antistatic property of the polyester fiber treated by the as-synthesized ATO products is enhanced remarkably. The triboelectricity voltage below 1.0 kV, half life below 1.0 s and surface resistance below 1.0×106 Ω can be attained.