AbstractDuring the production of epoxy resins, it is crucial to control or to know the epoxy groups. It is known that epoxy value is the most important analytical index of epoxy resin physical quantity to characterize the number of epoxy groups in epoxy resin. In this paper, two ways for testing the epoxy values of E44 epoxy resin are developed based on chemical titration method: hydrochloric acid‐acetone method and perchloric acid‐tetraethylammonium bromide method. The features of different methods and the influence of approaches on epoxy value are studied systematically. At the significant level of 0.05, for hydrochloric acid‐acetone method, the confidence interval for the mean is (0.454±0.003)eq/100 g, and for perchloric acid‐tetraethylammonium bromide method, the confidence interval for the mean is (0.453±0.003)eq/100 g. It has been proved that the test results of the two methods are basically the same. And the advantages and disadvantages of the two methods have been put forward. In addition, the testing mechanism of hydrochloric acid‐acetone method and perchloric acid‐tetraethylammonium bromide method is illustrated in detail. On the basis of superiority over the two methods, a novel method for testing epoxy resin with rapid and accurate epoxy value can be envisioned.