To study the effect of different high-voltage electric field polarisation treatment process parameters on the viability of seeds of dried chili peppers. In this study, a high-voltage electrostatic polarisation treatment system was constructed to carry out experiments on the effects of different high-voltage electric field polarisation treatment process parameters on the viability of dried chili seeds. Conduct one-way tests to determine the preferred polarisation method and the preferred interval for output voltage and polarisation time. Two-factor, five-level central combination test with output voltage and polarization time as test factors and seed conductivity as a response indicator. Determining the better combination of parameters for output voltage and polarization time; Conducting seed germination trials to validate the effectiveness of the polarisation process. The results of the one-way test showed that: Negative-voltage polarisation was more effective than positive-voltage polarisation and alternating positive–negative-voltage polarisation in promoting seed vigor, with a better output voltage in the range of 10–14 kV, and a better polarisation time in the range of 20–40 s; The results of orthogonal tests showed that: Under the condition of negative voltage polarisation treatment, the output voltage of 12.08 kV and polarisation time of 30.32 s was the better parameter combination, at which the seed conductivity was minimum 159.87 uS/(cm g). Analyzing the function of cell membrane selective semi-permeability by seed conductivity change and revealing the mechanism of seed viability enhancement by high voltage electric field polarisation treatment; In the seed germination test, compared with the control group, seed germination potential increased by 9.09%, germination rate increased by 20.45%, germination index increased by 3.49, and vigor index increased by 41.66 under high-voltage electrostatic polarisation treatment, and all vigor indexes were significantly improved. The results of this study can provide a basis for the selection of processes and parameters for subsequent high-voltage electric field polarisation treatment of crop seeds.