The characteristic impedance of a power line is an important parameter in power line communication (PLC) technologies. This parameter is helpful for understanding power line impedance characteristics and achieving impedance matching. In this study, we focused on the characteristic impedance matrices (CIMs) of the medium-voltage (MV) cables. The calculation and characteristics of the CIMs were investigated with special consideration of the grounded shields and armors, which are often neglected in current research. The calculation results were validated through the experimental measurements. The results show that the MV underground cables with multiple grounding points have forward and backward CIMs, which are generally not equal unless the whole cable structure is longitudinally symmetrical. Then, the resonance phenomenon in the CIMs was analyzed. We found that the grounding of the shields and armors not only affected their own characteristic impedances but also those of the cores, and the resonance present in the CIMs should be of concern in the impedance matching of the PLC systems. Finally, the effects of the grounding resistances, cable lengths, grounding point numbers, and cable branch numbers on the CIMs of the MV underground cables were discussed through control experiments.