Thermal aging of natural ester oil shows drastic reduction in partial discharge inception voltage (PDIV) and a significant variation is observed only above a certain aging time, under AC, DC, high frequency AC voltages and with harmonic voltages with different total harmonic distortion. Weibull distribution studies on PDIV measurements indicate a reduction in scale parameter (α) with increase in thermal aging temperature. A characteristic reduction in breakdown voltage was observed with the thermally aged ester oil, under AC, DC and standard lightning impulse voltage. The breakdown voltage variation with aged ester oil follows normal distribution. Ultraviolet (UV) analysis of ester oil thermally aged at 160°C has revealed a regular shift of the derived absorbance parameter to longer wavelengths. The interfacial tension and turbidity exhibits an inverse relationship with the thermally aged ester oil. Gas chromatography/mass spectrometric analysis of the thermally aged ester oil predicted the formation of more carboxylic acids and ketones with aging duration. The steady-state fluorescence on thermally aged ester oil exhibits a shift in its emission profile, which is in tandem with the UV absorption spectroscopic analysis. Fluorescence analysis can be adopted as a real-time monitoring tool in transformers, to understand the condition of liquid insulation. The viscosity dependence on the wavelength of derivative absorption maxima follows a direct relationship with the thermally aged natural ester oil. © 2020 Institution of Engineering and Technology. All rights reserved.