Three groups of neutron shielding experiments were set up to study the shielding performance of B4C/Al composite, using the Monte-Carlo method. We have made the following changes: the content of boron carbide 20%–40%, neutron energy 200 eV–15 keV, material thickness 0.3–2 cm, so that we can draw the conclusions: the content of boron carbide and neutron transmission coefficient show a linear relation, with a big drop; under the same neutron energy, the neutron-shielding qualities of simulated specimens are for better than polyethylene boron carbide at the same content of B4C and water, copper, and concrete at the same thickness; an exponential decline relationship is exhibited by material thickness and neutron transmission coefficient, which change greatly with the increase in unit material thickness; the content of boron affects the thermal neutron transmission coefficient seriously. In the thermal neutron energy region, the change of per unit neutron energy(100 eV) has a big influence on neutron transmission coefficient. In the slow neutron energy region, the influence is small.