Oil-pressboard/paper insulation materials are essential in transformers for ensuring their safe and stable operation, primarily due to their roles in spatial electric field distribution and charge migration mechanisms. Current spatial distribution analyses rely on computational methods that lack empirical validation, particularly for oil-pressboard/paper composites. This study leverages the principles of the Kerr electro-optic effect to develop a rapid measurement platform for electric fields within oil-pressboard/paper insulation under impulse voltage conditions, which measures the spatial electric field characteristics using Cu-Cu and Al-Al electrodes under various scenarios: with asymmetric and symmetric pressboard coverage and different numbers of insulating paper layers. Findings indicated: (1) In asymmetric pressboard models, Cu-Cu electrodes exhibit a consistent peak electric field of approximately 16 kV/mm, while Al-Al electrodes show peak values of 18.13 kV/mm and −14.98 kV/mm. Charge density patterns are similar, with Cu-Cu at about 68 μC/m2 and Al-Al at 11.2 μC/m2 and −124.8 μC/m2. (2) Symmetric models present consistent peak electric fields and charge densities for both polarities. (3) Increasing insulating paper layers elevates electric field strengths. Both electrodes show the similar peak field of about 17 kV/mm with differing paper layers due to higher charge injection from the Al electrode. (4) Utilizing the Schottky effect and field emission principles, the study clarifies charge generation and migration mechanisms. These insights could provide a theoretical foundation for designing and verifying oil-pressboard/paper insulation structures in transformers.