In this communication, we report our recent achievement in synthesis and self-assembly of both spherical and cubic PbTe nanocrystals using a high-temperature solution-phase synthesis approach. The possible mechanism of nanocrystalline evolution from spherical to cubic structure has also been discussed. It is possible to use the highly orientated PbTe nanocrystals as building blocks to achieve thickness-controlled film for further manipulation into thermoelectric devices.