In this paper, p-type thermoelectric material Te–Se solid solutions have been successfully prepared by the high-pressure technique. The thermal conductivity of Te was depressed sharply by Se alloying. An extremely low thermal conductivity ∼0.27 W m−1 K−1 was obtained for Te alloyed with 15 mol% Se, which near the theoretical minimum, κ min . The bipolar diffusion effect of Te was suppressed by Se alloying due to the increased band gap, which lead to enhanced Seebeck coefficient and depressed bipolar diffusion thermal conductivity under high temperature. The maximum figure of merit, ZT of 0.37 at 480 K was obtained for Te alloyed with 5 mol% Se, which is about twice higher than that of pristine Te.