Pb0.33Sn0.67Te is an important semiconductor thermoelectric material. It was successfully synthesized through a HVPG technique. The growth temperature and time are varied in the range of 1000 °C–1200 °C and 4–8 h, respectively. A 2k factorial design of experiments is used to study the effect of material thermoelectric performance (ZT). Investigations revealed that maximum ZT of 0.084 can be achieved at 1200 °C growth temperature of and 4 h anneal time of. The crystals showed high ZT value, which is likely to have contributed to the ZT enhancement. It showed that Pb0.33Sn0.67Te manufactured via HVPG applied for thermoelectric applications.