We report on the interplay between nanostructuring and defect activation in dense polycrystalline Bi₂Te₃ thin films in terms of the thermopower engineering. The Bi₂Te₃ thin films were prepared at relatively low temperatures (100–160 °C) by atomic layer deposition and their grains showed different sizes in the range of 50–200 nm according to the deposition temperatures. We monitored the conductivity, Seebeck coefficient, and power factor of all samples from the temperature of 50–400 K. By increasing the growth temperature, remarkably, we observed the gradual defect activation from the nominal p-type to n-type in our binary end compound, Bi₂Te₃ without any alloying. The present results give us an insight on the optimization of thermoelectric materials not only by nanostructuring (i.e., phonon engineering) but also by controlled defect activation (i.e., electron engineering).