γ-ray, fast and thermal neutrons shielding features for five Pb-free {[(TeO2)0.70(B2O3)0.30]0.7 (ZnO)0.30}(1-x)(La2O3)x (x = 0.01, 0.02, 0.03, 0.04, and 0.05 mol%) glasses have been inspected in this work. For all samples, within the photon energy range of 0.015–15 MeV, linear attenuation coefficients (μ) and mass attenuation coefficients (μ/ρ) were estimated using WinXCOM program (theoretical approach), and obtained μ/ρ values are in fine agreement with computed μ/ρ results of respective MCNP5, Geant4, and Penelope codes. By utilizing μ/ρ values of WinXCOM, γ-ray attenuation parameters like effective atomic number (Zeff), effective electron density (Neff), half-value layer (HVL), and mean free path (MFP) were assessed within 0.015–15 MeV photon energy range, for all samples. Additionally, exposure buildup factors (EBFs) and energy absorption buildup factors (EABFs) were calculated for all samples by applying a five parameter geometric progression (G‒P) fitting method as a function of various penetration depths (1, 5, 10, 15, 20, 25, 30, 35, and 40 mfp) within 0.015–15 MeV photon energy range. The derived radiation protection efficiency (RPE) results indicate all samples' effective attenuation competence for lower energy γ-rays. Among all glasses, 46.55TeO2-19.95B2O3-28.5ZnO–5La2O3 (mol%) sample, by having relatively bigger μ/ρ and Zeff, minimal HVL and MFP, and lowest EBF and EABF, endorse its' excellent γ-ray shielding effectiveness. Further, neutron shielding parameters such as macroscopic removal cross-section for fast neutrons (ΣR), coherent and incoherent scattering cross-sections (σcs & σics), absorption cross-section (σA), and total cross-section (σT) for thermal neutrons were explored. By using the Geant4 code, ‘σT’ values have been deduced within 10−4‒10−8 MeV neutron energy range. The 46.55TeO2-19.95B2O3-28.5ZnO–5La2O3 (mol%) glass owns relatively larger ΣR (0.1474 cm−1) for fast neutrons attenuation and ‘σT’ (10.1444 cm−1 at 0.0253 eV neutron energy, 15.9824 cm−1 → 0.551 cm−1 from 1 × 10−8 MeV →1 × 10−4 MeV neutron energy) for thermal neutrons absorption, respectively, revealing its' superior neutrons shielding ability.