Impact of thermal ageing of pressboard material in transformer oil containing dibenzyl disulphide (DBDS) under different ambience, such as air, N2, He and vacuum has been studied to understand the level of copper sulphide diffusion. The characteristic variations in electrical and thermal properties of copper sulphide diffused oil impregnated pressboard (OIP) material have been measured under different ageing conditions. Surface charge accumulation studies with AC and ±DC voltages showed that surface charge decay time was longer in air aged OIP material. Surface discharge studies by adopting ultra-high frequency (UHF) sensing indicated a reduction in the SDIV with the level of ageing although the characteristic variation in flashover voltage (FOV) under lightning impulse (LI) voltage is almost the same. Also the SDIV reduced with increase in frequency of supply voltage. Thermo-gravimetric analysis (TGA) indicated that maximum weight loss temperature (Tmax) of the cellulose constituent of OIP material decreased with ageing. Laser induced breakdown spectroscopy (LIBS) was adopted to quantify the diffused copper sulphide contaminant in OIP material and the results were compared with the inductively coupled plasma (ICP) spectroscopy based analysis. Based on these studies, deteriorating effect of ageing medium on several properties of OIP material was understood. © 1994-2012 IEEE.