Power transmission technology plays an important role in energy sustainability. Bushing is an indispensable type of equipment in power transmission. In production, the accelerator changes the temperature distribution during the curing process, influencing the formation of defects and thus the safety output of renewable energy. In this study, uncured epoxy resin samples with different accelerator contents were prepared and measured by differential scanning calorimetry (DSC). The obtained heat flow curves were analyzed for curing kinetics. Then, the curing process of large length–diameter ratio bushings was simulated by using the finite element method combined with a curing kinetics model, transient Fourier heat transfer model, and stress–strain model. The study reveals that the curing system can be established by the Sestak–Berggren autocatalytic model with different accelerator contents. The overall curing degree and the maximum radial temperature difference of the capacitor core tend to increase and then decrease with the accelerator content. This is mainly attributable to the rapid exotherm excluding the participation of some molecular chains in the reaction, resulting in permanent under-curing. As the accelerator content increases, the strain peak decreases and then increases. This paper provides guidance for the comprehensive evaluation and manufacturing of the low-defect capacitor cores of large-size high voltage direct current (HVDC) bushings.