The neutron radiation was often encountered in a wide range of the industries, such as aerospace, healthcare industry and nuclear power plants, and it was an arduous challenge to shield the neutron radiation to protect the human health and equipment safety. In order to fabricate effective neutrons shielding material, the alternating multilayered (high density polyethylene)/(high density polyethylene/ boron nitride) (HDPE/(HDPE/BN)) and (HDPE/BN)/(HDPE/Barium sulfate (BaSO4)) composites were fabricated through a multilayered co-extrusion system. The HDPE/BN layers in the alternating multilayered HDPE/(HDPE/BN) and (HDPE/BN)/(HDPE/BaSO4) composites had a continuous and layered distribution structure, and the BN particles oriented along the extrusion direction. Moreover, the collision probability between incident photons and flake-shaped particles will be enhanced through alignment of the oriented BN particles. Therefore, the neutron transmittance was obviously decreased with increasing the layer number. Meanwhile, Compared to the traditional polymer blended materials, the alternating multilayered composites showed an excellent shielding efficiencyIn addition, the results of dynamic rheological analysis showed the alternating multilayered composites with high layer number can weaken the cross-linking effects induced by secondary radiation. Furthermore, the BaSO4 was effective to shield the secondary radiation so that average melting point in nanoscale (Nano- Tm) ((HDPE/BN)/(HDPE/BaSO4)) ˃ Nano- Tm (HDPE/(HDPE/BN)) that was obtained through Nano-TA analysis.