Given their substantial neutron capture cross-section, extreme hardness, and high chemical and thermal stability, boron-based materials are widely used as building blocks to protect against highly ionizing radiations such as gamma rays and neutrons. Indeed, uncontrolled nuclear radiation exposure can be highly hazardous to radiation workers and the public. In this sense, this work presents an extensive study and experimental evaluation of the nuclear shielding features of hexagonal-boron nitride (h-BN) based nanocomposite, where bisphenol-A based polybenzoxazine (BA-PBz) was used as matrix. The neutron shielding studies were carried out at the nuclear research reactor of Algeria NUR. The surface treatment of h-BN nanoparticles was confirmed by FTIR and XPS techniques. The curing behavior and the degradation phenomena of the nanocomposites were evaluated by DSC-TGA analyses. The distribution of h-BN nanoparticles within the polymer matrix was assessed by TEM and SEM. The results showed that the developed boron nitride-based nanocomposite exhibits intriguing shielding performances and good thermal stability. The DSC-TGA tests exhibit high degradation temperature that reach 279°C. The highest performances were obtained at an h-BN concentration of 7 wt%, where the macroscopic cross was found to be (Σ = 3.844 cm^–1) with a screening ratio of (S = 96.12%), equivalent to a mean free path (λ) of 0.138 cm.