Grain size refinement is the vital stratagem for improving mechanical properties of Bi₂Te₃-based thermoelectric material. However, the donor-like effect induced by grain size refinement seriously deteriorates the thermoelectric properties especially near room temperature. Once the donor-like effect is generated, it is very difficult to eliminate the donor-like effect by the simple heat treatment process and other processes. In this study, the influences of particle size on the donor-like effect and thermoelectric properties are systematically studied for Bi₂Te₃-based compounds. As the particle size decreases, the donor-like effect is enhanced significantly. The oxygen-induced donor-like effect dramatically increases the carrier concentration from 3.36× 10¹⁹ cm^–3 for 10 M sintered sample to 7.33×10¹⁹ cm^–3 for 120 M sintered sample, which is largely beyond the optimal carrier concentration of 2.51×10¹⁹ cm^–3 and seriously deteriorates the thermoelectric properties. However, when the particle size of the powder is 1–2 mm, the Seebeck coefficient of –195 μV/K and the carrier concentration of 3.36×10¹⁹ cm^–3 near room temperature are achieved, which are similar to those of the ZM sample with the Seebeck coefficient of –203 μV/K and the carrier concentration of 2.51×10¹⁹ cm^–3. The powders without the obvious donor-like effect can be used as the excellent raw material for powder metallurgy process. A maximum ZT value of 0.75 is achieved for the 18 M sintered sample. The excellent thermoelectric properties are expected to be obtained by enhancing the texture further. This study provides a new way to regulate and effectively suppress the generation of the donor-like effect, and provides an important guidance for the preparation of materials with excellent thermoelectric and mechanical properties by powder metallurgy process.