Herein, the effect of multilayer core-shell-structured Zn/ZnO/Al2O3 particles on thermal conductivity and dielectric properties of epoxy composites was investigated. The core-shell-structured Zn/ZnO particles were obtained by a simple calcination method, and the multilayer core-shell-structured Zn/ZnO/Al2O3 particles were prepared using hydrolysis process. The Zn/ZnO/Al2O3/epoxy composites were fabricated, and atomic force microscopy (AFM) images showed that the fillers were well distributed in epoxy matrix. Thermal conductivity of Zn/ZnO/Al2O3/epoxy composites increased 178% by adding 12.0wt% of Zn/ZnO/Al2O3 particles. The dielectric constant of composites increased obviously with the increased content of Zn/ZnO/Al2O3 particles, while the dielectric loss is still low. These results illustrate that the combination of the thermal and dielectric properties tuned by multilayer core-shell particles gives potential application in extended domains for epoxy composites.