The paper presents some case spectral analysis of zero-sequence voltages and currents in an example industrial power distribution network. The network layout is based on typical power delivery networks in underground coal mines. Ground fault simulations have been made using an ATP/EMTP program. Due to the high environmental risks, the reliability of the protection relay operation related to their selectivity plays an important role. This paper tries to find the reasons for nonselective operation and unnecessary tripping in extensive mine cable networks, particularly with large power sources of higher-order harmonics. It was found that in transient states—due to the decaying oscillations occurring in complex RLC circuits—the results of short time measurements of the criterion values for ground fault protective relays can be overestimated (particularly for small values of ground resistance) and lead to nonselective tripping of a healthy cable line. Therefore, it might be advisable to increase the integration time used for measuring rms values. Also, if there is a significant level of higher harmonics in the industrial network generated by high-power converters, it should be noted that the higher harmonics of the ground fault current and currents measured by ground fault protection relays assume much higher values, which may also cause nonselective tripping. In this case, it may be advisable to use higher harmonic filters in the measuring circuits and to select a sufficiently high sampling frequency in the digital protective relays.