The current study focused on investigating the gamma-ray shielding capacity of nano sized CeO2 (nCeO2) doped vinyl ester composites (VE/nCeO2) produced by the direct pouring method with different nCeO2 contents ranging from 2.5 to 20 wt%. X-ray Diffraction and Transmission Electron Microscopy were used to characterize the structural properties of nCeO2 particles. The gamma radiation shielding performance of the produced composites was investigated experimentally and theoretically within the scope of primary shielding coefficients like mass attenuation coefficient, half value layer, tenth value layer, mean free path, effective atomic number, and effective electron density. The experimental studies were obtained by NaI(Tl) scintillator detector for gamma-ray energies coming from Ba-133, Cs-137, and Co-60 radioactive point sources in the narrow beam geometry. The outcomes were compared with the theoretical calculations acquired by Monte Carlo N-Particle Transport version 6 code. The effective atomic number and effective electron density studies were additionally examined with WinXCom software. A good consistency between the experimental and theoretical outcomes was achieved. It was determined that among all composites, VE/20%nCeO2 composite having maximum nCeO2 content showed the best radiation shielding performance against all energy values. The nCeO2 additive was successful in enhancing the radiation attenuation performance of vinyl ester, and mass attenuation coefficients of investigated samples gradually changed from 0.15 to 0.79 cm2/g at 81 keV. The gamma-ray attenuation coefficients of the composites were compared with traditional shield materials and previously studied shielding materials and evaluated as promising lightweight, non-toxic alternatives for the low-energy gamma-ray shielding applications.