The lifespan of an electrical transformer, primarily determined by the condition of its solid insulation, is well known under various operating conditions when mineral oil is the coolant in these machines. However, there is a trend toward replacing this oil with biodegradable fluids, especially esters; therefore, an understanding of the ageing of solid insulation with these fluids is essential. Currently available data do not allow for the selection of the best ester among those available on the market, as each study applies different conditions, making it impossible to compare results. Thus, this paper analyses the degradation of Kraft and Thermally Upgraded Kraft papers with the following five most promising commercial esters: sunflower, rapeseed, soybean, palm, and synthetic. The materials underwent accelerated thermal ageing at 130, 150, and 170 °C, and the integrity of the papers was evaluated through their polymerisation degree and the obtaining of the degradation kinetic models. The wide range of materials studied in this work, which were subjected to the same treatments, allows for a comparison of the esters, revealing significant differences in the impact of the alternative fluids. Sunflower, rapeseed, and soybean esters provided the best paper protection, i.e., the degree of polymerisation of Kraft paper in the tests at 150 °C decreased by 71% with these fluids, compared to the 83% reduction with mineral oil, 79% reduction with palm ester, and 75% reduction with synthetic ester. Furthermore, different kinetic models were obtained to predict the degradation; it was concluded that the Emsley model provides the best fit. Additionally, it was found that the behaviour of a dielectric fluid with one type of paper cannot be extrapolated, which is only noticeable in broad-scope studies.