The Ba(Ti,Zr)O-3-based multilayer ceramic capacitors (MLCCs) with Ni electrodes, which meet the Electronic Industry Association Y5V standard (from -30 degrees to 85 degrees C, at a temperature capacitance coefficient between -82% and 22%), have been studied in view of the electrode-ceramic inter-diffusion by several microstructual techniques (scanning electron microscopy/transmission electron microscopy/high-resolution transmission electron microscopy (HRTEM)) with an energy-dispersive X-ray spectrometer (EDS). The EDS analysis shows that the elements' inter-diffusion took place along the metal-dielectric interface and the migration of Ni toward the dielectric layers dominated this process. The incorporation of Ni did not transform the crystal structure but introduced lattice distortions, which were characterized by HRTEM, X-ray diffraction, and EDS. The degree of Ni diffusion in the sample with the thinner dielectric layer was more severe. It was concluded from the results that the Ni diffusion is related to the formation of oxygen vacancies after the annealing process, which should be a noticeable factor in the degradation behavior and reliability of base metal electrode MLCCs. The factors influencing the inter-diffusion are also discussed.