Because of the high global warming potential of SF6 gas, research on alternative gases for electrical insulation with a lower environmental impact is essential. Gas mixtures composed of electronegative gases and N2 gas have the advantage of the reduction of the amount of SF6 gas and of utilizing the synergistic effect in electrical insulation performance. We investigated the partial discharge (PD) and breakdown (BD) characteristics of SF6/N2 and PFC (C3F8/N2 and C2F6/N2) gas mixtures under non-uniform electric field conditions, by changing the dilute content of electronegative gases. As a result, the synergistic effect in SF6/N2 gas mixtures was verified to be higher than that in PFC/N2 gas mixtures. The physical mechanism from PD inception to BD was discussed with consideration of the difference in electronegativity of SF6 and PFC gases. Furthermore, we found that PD inception and PD-to-BD mechanisms changed at a content of 10 ppm for SF6 due to the electron attachment activity of SF6 gas. The change in the PD and BD mechanisms in C3F8/N2 and C2F6/N2 gas mixtures appeared at 0.1% content for C3F8 and at 1% content for C2F6.