Charge accumulation in the insulating oil-paper system determines the operating safety of the converter transformers in high-voltage direct current (HVDC) transmissions. However, it has been a long-standing challenge to reveal the charge distribution of the electric double layer (EDL) at the insulating oil-paper interface and relate it to charge transport. In particular, the EDL and charging mechanisms at the oil-paper interface have not been fully understood. We herein demonstrate that the charge distribution of EDL at the oil-paper interface is probed through Kelvin probe force microscopy (KPFM). The origin charge distribution of EDL without any additives shows that the negative charge gathers on the insulating paper surface, while the positive charge diffuses in the insulating oil, which is derived from the electron affinity difference between insulating oil and insulating paper and acts as an additional obstacle to charge transportation at the oil-paper interface. Interestingly, the additive 3-amino-2,4-triazole (ATA) can tune the charge distribution of EDL by bringing extra hole traps, which significantly decreases the interface barrier and reduces the charge accumulation at the oil-paper interface. As well as increasing charge mobility in oil-paper insulation, ATA also ensures stabilization of operation under polarity inversion conditions by accelerating the dissipation rate of accumulated charge.