The Bi4Te3 films with well-ordered orientation and microstructure were successfully prepared on SiO2 substrate by a vacuum thermal evaporation deposition technique for the first time. We discussed the effects of evaporation temperature and substrate temperature on the phase and its well-ordered growth of Bi4Te3 films. The formation of Bi4Te3 phase is owing to the differences of the saturated vapor pressure. The thermoelectric transport properties of the Bi4Te3 films were investigated and the (00l)-oriented nanopillars array film has a better electrical transport performance, whose value of PF is 0.032 mWm−1 K−2 at 339 K, approaching twice that of the non-oriented ordinary film. The enhanced electrical properties of Bi4Te3 films could be achieved via the high-crystallinity well-controlled (00l)-oriented nanopillars array.