Abstract: This paper aims at dispersing nano Al₂O₃ in polyethylene(PE) and ethylene vinyl acetate copolymer (EVA) blends to build thermal conductive composites with high local particle concentration and selective distribution structure. With nano Al₂O₃ as thermal conductive filler, PE and EVA as matrix resin, Al₂O₃/PE-EVA thermal conductive composites were prepared by melt blending method. The phase structure of PE-EVA blends and distribution of Al₂O₃ in blends were investigated by selective solution extraction method and SEM. The thermal conductivity and mechanical properties of Al₂O₃/PE-EVA composites were evaluated. The results show that blends with two-phase co-continuous structure are obtained at PE to EVA mass ratio of 1:1. By introducing Al₂O₃ into PE-EVA two-phase co-continuous blends, Al₂O₃ is mainly dispersed in PE phase. The distribution behavior of Al₂O₃ and the formation of co-continuous structure are helpful to improve the thermal conductivity of composites. 21.2% increase of thermal conductivity is obtained for Al₂O₃/PE-EVA composites with selective distribution and co-continuous structure, in comparison to that of Al₂O₃/PE composites at Al₂O₃ mass fraction of 50%. With the increase of Al₂O₃ mass fraction, the tensile strength of Al₂O₃/PE-EVA composites tends to be similar to that of Al₂O₃/PE composites. The elongation at break of Al₂O₃/PE-EVA composites is also superior than that of Al₂O₃/PE composites thanks to the toughing effect of EVA phase.