This study aims to develop a correlation equation between a porous electrode structure and the effective conductivity so as to design an optimal structure for a thick electrode layer of a high-capacity battery. We carried out a three-dimensional reconstruction of a lithium cobalt oxide and graphite electrode based on the cross-sectional images obtained via focused ion beam-scanning electron microscopy (FIB-SEM). The Li ion and electron conductivities are evaluated based on the effective conductive path determined from simulation and these values are compared with the experimental results obtained by electrochemical impedance spectroscopy carries out with a symmetric cell and the direct conductivity measurement under compression. Moreover, the amount of binder and the diameter of the active material particles are increased and decreased numerically using an actual reconstructed electrode structure, and the effect of those structures on the effective conductivity is examined. The most dominant factors that degrade ionic conductivity are the binder distribution and the particle morphology, respectively, in the cathode and anode, and a correlation equation with the function of porosity is obtained. These values are compared with those obtained by theoretical model equations, and the difference between the current effective ionic conductivity and the physical limiting value is determined.