The new glasses with the chemical formula 45 P2O5 – 25 ZnO – (30-x) Li2O – xMoO3 (where x = 1,3,5, and 7 in mol%) have been fabricated using the melt quenching method. The amorphous nature was not changes before and after gamma irradiation by X-ray diffraction. The effect of gamma radiation (60Co) with the dose rate of 20k Gray on different properties of glasses has been studied. The Raman spectra were recorded between 400 and 4000 cm−1 wave number range to study the structural variation of the sample. The intensity of the Raman spectra is increases and peaks are shifted towards to left due to structural disorder. Intensity of the photoluminescence spectra emission at 287 nm and 390 nm and the excited at 240 nm wavelengths decreases after gamma irradiation. The obtained results confirms the shielding features of the glass when compared to other referenced glass material. The presently studied glass is excellently stable and can withstand high gamma ray doses and these glasses are suitable for radiation applications.