The transformer is a core device of the power system, and it is generally considered that the aging of insulating paper is important to the transformer. The aging process of insulating paper is the degradation process of cellulose. If it can be detected regularly, the aging of oil–paper insulating systems can be monitored conveniently. 5‐hydroxymethylfurfural is an important chemical substance produced by cellulose decomposition. It has broad prospects because of its many advantages. The oil–paper insulation system was thermally aged at 80, 90, 100, and 110 °C to measure the concentration of 5‐hydroxymethylfurfural on insulating paper and in transformer oil. In this paper, the concentration of 5‐hydroxymethylfurfural is detected by high‐performance liquid chromatography. The linear correlation coefficient of this method can reach 0.99, and the minimum detected concentration can be reduced to 10 µg/l. Experiments show that the concentration of 5‐hydroxymethylfurfural increases with the aging time, and when degree of polymerization (DP) decreased, the concentration of 5‐hydroxymethylfurfural increased. The correlation coefficient is greater than 0.92, which shows that there is an experimental relationship between the concentration of 5‐hydroxymethylfurfural and DP. The parameters of regression curves are different at different temperatures, but in actual operation, the temperature is low and remains stable. Therefore, 5‐hydroxymethylfurfural is expected to be a new indicator of the aging degree of oil–paper insulation system. © 2020 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.