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Particle-reinforced composites are widely applied as nuclear radiation shielding materials for their excellent comprehensive properties. The work aimed to calculate the influence of the functional reinforced particles spatial arrangement on the neutron shielding performance of composites and attempted to explain the influence mechanism by investigating the neutron flux distribution in the materials. Firstly, four suitable physical models were established based on the Monte Carlo Particle Transport Program (MCNP) and mathematical software MATLAB, namely the RSA (Random Sequential Adsorption) Model with particles random arrangement and FCC Model, BCC Model and Staggered Arrangement Model (SA Model) with particle periodic arrangements. Later, based on these four physical models, the neutron transmittance of two kinds of typical B4C reinforced composites, 316 stainless steel matrix composite and polyethylene matrix composite, were calculated under different energy neutrons sources (0.0253 eV, 50 eV, 50 keV, fission spectrum, 241Am-Be spectrum and 14.1 MeV) and the neutron flux distribution in the 316 stainless steel composite was also analyzed under 0.0253 eV neutron and fission neutron sources. The results indicated that the spatial arrangement of B4C has an impact on the neutrons shielding performance of the composite and the influence changes with neutron energy and B4C content. It can be concluded that the RSA model and the periodic arrangement models can be used in different calculation cases in the future.