Cellulosic pressboard is a key insulation material in oil filled transformers. Surface discharge or partial discharge degrades the insulation material and reduces the life time of the transformer. This study is aimed at understanding the effect of thermal aging of pressboard on the variation of its surface discharge and chemical characteristics. Thermal degradation of pressboard was carried out at 180 °C for 500 h in presence of ester oil under simulated aging conditions. The variation of salient electrical characteristics like surface discharge inception voltage (SDIV), charge measurement and optical emission spectra of the discharges were assessed at different aging periods. A significant reduction in SDIV was observed due to thermal aging. The charge measurement indicated that total charge deposition on pressboard increased with aging duration. Optical emission spectroscopy yielded valuable information regarding the elements evolved during discharge activity. Chemical characterization of the virgin and aged pressboard samples was carried out using analytical pyrolysis coupled with gas chromatograph-mass spectrometric technique (Py-GC/MS). The production of anhydrosugars, furan derivatives and oxygenates from the pressboard increased with aging time, while the esters in the oil were degraded to carboxylic acids with aging. Owing to the weakening of the hydrogen bonding network in oil impregnated pressboard with thermal ageing, high yield of end-chain depropagation products like anhydrosugars was observed during pyrolysis. The weak sites in cellulosic pressboard are expected to act as charge deposition sites. © 2017, Springer Science+Business Media B.V.