Tape casting and electroless plating were used to fabricate Al2O3/Ni laminar ceramic composites with close control of the thickness of the Al2O3 and Ni layers. Ninety-seven percent relative density, macrodefect-free composites were obtained by spark plasma sintering. In electroless plating solutions, the stable potential of grain boundary led to the first deposition of nickel on the grain boundary of Al2O3. Scanning electron microscopy, energy-dispersive X-ray, and X-ray diffraction were used to analyze the structure, elements distribution, and phase composition of the Al2O3/Ni laminar composites.