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SnxSb20Se80−x chalcogenide alloys (with x = 8, 10, 12, 13.5, 15, 16.5 and 18 at.%) were prepared by the melt quenching technique. The average coordination number and the overall mean bonding energy were calculated. The x-ray diffraction studies revealed that the alloys with x = 8 and 10 at.% were amorphous and the alloy with x = 12 at.% was partially crystalline whereas the alloys with x = 13.5, 15, 16.5 and 18 at.% were crystalline. The glass transition temperature, the crystallization temperature, the melting temperature and the glass-forming tendency of the amorphous samples were determined from the differential scanning calorimetry measurements. The glass transition activation energies and the crystallization activation energies were determined using Kissinger as well as Augis and Bennett methods. Upon annealing the bulk amorphous samples at 573 K, two different crystalline phases, SnSe2 and Sb2Se3, were observed. X-ray reflectometry analysis revealed that the surface roughness increased with increasing annealing temperature. The density of the as-prepared films increased with increasing Sn content. Upon annealing at 523 K the density increased, whereas the density of most of the films decreased upon annealing at 573 K. Thermal gravimetric analysis showed a steeper weight loss upon heating after 533 K.