Pb–Sn–Te bulk nanocrystalline (NC) materials are prepared successfully by quenching melts under high pressure. The mean particle size is about 100 nm and the crystal structure is NaCl type. The mechanism of formation of the bulk NC alloy is explained: there is an increasing of the nucleation rate and a decrease in the growth rate of nuclei with increase of pressure during the solidification processes. The thermoelectric properties of Pb–Sn–Te bulk NC alloy are enhanced. This method is promising for producing thermoelectric materials with improved high-energy conversion efficiency.