solid solutions with x = 0:2, 0.25 and 0.3 − p type thermoelectric compounds with an excess of Tellurium dopant up to 4 wt% were crystallized. By increasing the Bi2Te3 content in the Bi-Sb-Te system, the hole concentration decreased and in consequence caused an optimum Seebeck coefficient and a decrease in electrical conductivity and thermal conductivity, thus resulting in an increase in the figure of merit at x = 0:25. The results showed that optimum thermoelectric properties can be achieved for a mixture of x = 0:25 with 3 wt% Te added. Structural characterizations of this compound in the absence and presence of the dopant were carried out by means of X-Ray diffraction measurement, scanning electron microscopy, electron backscattering diffraction and atomic force microscopy. Detailed analyses confirm that the improvements in thermoelectric parameters due to the intrinsic structure and minimum defects during crystallization of the compounds result from the excess of Te.