Poor wettability and weak interfacial bonding between Cu and Al2O3 have been critical issues for sintering of high-quality Ni@Al2O3/Cu composites. In this paper, we explore an interfacial engineering design methodology to achieve good mechanical properties of Ni@Al2O3/Cu composites using spark plasma sintering method. The Ni coated powders were prepared using a heterogeneous precipitation method, which can significantly improve wettability between Cu and Al2O3 and enhance their interfacial bonding. The sintered Ni@Al2O3/Cu composites with a copper content of 15 vol% showed a compact network structure of alumina well-infiltrated with metallic Cu, and achieved good mechanical (e.g., fracture toughness of 6.72 MPam1/2) and physical properties (e.g., relative density of 99.3% and electrical resistivity of 1.2810−3 Ω m). The key mechanisms for the enhanced properties of the composites synthesized using the Ni coated composite powders have been identified as: (1) well-formed ceramic/metal interfacial structures which improve wettability of Al2O3 with Cu, and promote the formation of a homogeneous network structure; (2) enhanced elemental diffusion and interfacial reactions, which result in formation of Cu2O and CuAlO2 and thus improve interfacial wetting and bonding properties.