Bulk samples of Sn10Sb20-x Bi (x) Se-70 (0 a parts per thousand currency sign x a parts per thousand currency sign 8) chalcogenide alloys were prepared by the conventional melt quenching technique. Thin films were prepared on well-cleaned glass substrates by thermal evaporation technique. X-ray diffraction studies revealed that the alloys with x = 0 and 2 at.% of Bi were amorphous, whereas the alloys with x = 4, 6, 8 at.% were crystalline. The crystalline phases are identified as due to the formation of Bi2Se3 and BiSe2 phases. The microstructural and differential scanning calorimetric studies show the presence of these phases. A simple, straight forward procedure suggested by Swanepoel has been used to calculate the optical parameters, refractive index, and extinction coefficient. The optical gap for all the samples has been obtained from the Tauc plots. The variation in optical parameters for different Bi concentration has been explained on the basis of presence of defect states and the change in stoichiometry with the change in Bi concentration.