Three distributions of boron nitride (BN) particles were designed: random, oriented, and periodic. The BN particles in multilayered high-density polyethylene/boron nitride (HDPE/BN) composites were oriented along the extrusion direction and arranged regularly, and the BN/HDPE layers containing oriented BN particles exhibited periodic distribution in multilayered HDPE/(HDPE/BN) composites. Compared to the random distribution of BN particles, these structures could help reduce neutron transmittance and improve the linear and mass attenuation coefficients. Moreover, the neutron shielding efficiency could rapidly improve as the number of layers of the multilayered composites increased. Meanwhile, the crosslinking effect of the HDPE matrix caused by secondary radiation could be weakened as the number of layers of the multilayered composites increased. This study also introduced a novel idea for designing neutron shielding materials. POLYM. ENG. SCI., 59:E348-E355, 2019. (c) 2019 Society of Plastics Engineers