Selenium doped thin films of GeTe alloys were investigated for their structural modifications by X-ray Diffraction, Fourier Transform Infrared Spectroscopy, X-ray photoelectron Spectroscopy (XPS) and Raman Spectroscopy. The band gap increase from 0.69 to 1.10 eV with increasing Se addition signifies the possibility of band gap tuning in the material. Disorder decreases, band widens and conductivity saturates about 0.20 at.% of Se addition. Structural changes are explained by the bond theory of solids. The as-deposited films are amorphous and 0.50 at.% Se alloy forms a homogeneous amorphous phase with a mixture of Ge-Se and Te-Se bonds. The XPS core level spectra and Raman spectra investigation clearly indicate the formation of Ge-Se, GeTe2 and Te-Se bonds with Se addition. Crystallization temperature is found to be increasing with Se and the 0.10 at.% Se alloy is found to have a higher resistance contrast compared to other Se concentration alloys. Up to 0.10 at.% of Se addition can enhance GeTe phase change memory properties. (C) 2013 Elsevier B.V. All rights reserved.