N-type bismuth telluride (Bi2Te3) thin films were prepared on an aluminum nitride (AlN)-coated stainless steel foil substrate to obtain optimal thermoelectric performance. The thermal co-evaporation method was adopted so that we could vary the thin film composition, enabling us to investigate the relationship between the film composition, microstructure, crystal preferred orientation and thermoelectric properties. The influence of the substrate temperature was also investigated by synthesizing two sets of thin film samples; in one set the substrate was kept at room temperature (RT) while in the other set the substrate was maintained at a high temperature, of 300 °C, during deposition. The samples deposited at RT were amorphous in the as-deposited state and therefore were annealed at 280 °C to promote crystallization and phase development. The electrical resistivity and Seebeck coefficient were measured and the results were interpreted. Both the transport properties and crystal structure were observed to be strongly affected by non-stoichiometry and the choice of substrate temperature. We observed columnar microstructures with hexagonal grains and a multi-oriented crystal structure for the thin films deposited at high substrate temperatures, whereas highly (00 l) textured thin films with columns consisting of in-plane layers were fabricated from the stoichiometric annealed thin film samples originally synthesized at RT. Special emphasis was placed on examining the nature of tellurium (Te) atom based structural defects and their influence on thin film properties. We report maximum power factor (PF) of 1.35 mW/m K2 for near-stoichiometric film deposited at high substrate temperature, which was the highest among all studied cases.