Natural ester is considered to be a substitute of mineral oil in the future. To apply natural ester in large transformers safely, natural ester impregnated solid insulation should be proved to have comparable dielectric strength and thermal stability to mineral oil impregnated solid insulation. This paper mainly focuses on a comparative study of physicochemical, ac breakdown strength and thermal stability behavior of BIOTEMP natural ester/pressboard insulation and Karamay 25# naphthenic mineral oil/pressboard insulation after long term thermal ageing. The physicochemical and dielectric parameters including moisture, acids and the ac breakdown strength of these two oil/pressboard insulation systems at different ageing status were compared. The permittivity and ac breakdown strength of these two oil/pressboard insulation systems at different temperatures were also investigated. And a comparative result of the thermal stability behavior of these two oil/pressboard insulation systems with different ageing status was provided at last. Results show that though natural ester has higher absolute humidity and acidity during the long ageing period, the lower relative humidity of natural ester helps to keep its ac breakdown strength higher than mineral oil. The pressboard aged in natural ester also has higher ac breakdown strength than that aged in mineral oil. The lower relative permittivity ratio of natural ester impregnated paper to natural ester is beneficial to its dielectric strength. Using natural ester in transformer, the resistance to thermal decomposition of the oil/pressboard insulation system could be also effectively improved.Index Terms -Natural ester, mineral oil, pressboard, physicochemical, dielectric strength, thermal stability.