In the present investigation, nuclear radiation shielding parameters of xTeO2 + (100–x)Li2O (where x = 95, 90, 85, 80, 75, and 70 mol%) glass system have been examined. Gamma shielding parameters such as mass attenuation coefficients (MAC), half-value layer (HVL), tenth-value layer (TVL), mean free path (MFP), effective atomic number (Zeff), effective electron density (Neff) were calculated. Moreover, neutron effective cross sections (∑R) are determined. The calculations for present materials have been performed in different photon energy ranges (0.01–20 MeV) and using Monte Carlo N-Particle eXtended (MCNPX) simulation code and theoretical results were also obtained with WinXcom program. The results obtained from the MCNPX and WinXcom program were found to be in well harmony. Moreover, for the assessment of radiation shielding success of tellurite glasses, the mass stopping power (MSP) and projected range (PR) were computed for proton and alpha particles using stopping and range of ions in matter (SRIM) code. When the results obtained from the study are examined, it is seen that 95TeLi glass has the lowest HVL, TVL, MFP, TF and the highest (∑R) values. Therefore, the 95TeLi glass has the most perfect radiation shielding achievement than other investigated glasses. [ABSTRACT FROM AUTHOR]