Photoelectric characteristics are an important reference for high-voltage discharges and are closely related to the excited mode of the high-voltage source. In this paper, we built a large-scale volume dielectric barrier discharge (DBD) system, which is composed of multilayer parallel-plate DBD electrodes and is excited by a high-voltage source in the power density modulation (PDM) mode. Subsequently, we analyzed the applied energy equation and evaluated the DBD systems photoelectric characteristics. The results show that the energy values of different applied voltage cycles during a PDM period exhibit significant differences. However, the average energy in a PDM period is approximately constant. Moreover, the equivalent capacitance of the DBD cell is a function of both the applied voltage and energy density. For the DBD cell, with the increase in both the applied voltage and energy loaded on the DBD cell, the total equivalent capacitance (C) is approximately constant, the dielectric capacitance (C d ) increases exponentially and decreases linearly, while the discharge gap capacitance (C g ) decreases and increases in the same cases. In addition, the relative intensities of the discharge emission increase and the energy efficiency ratios of the relative photoquantum yield of active species decline with the increase in both the applied voltage and energy density loaded on the DBD cell. The experimental results have been analyzed by evaluating the influence of the electrical parameters, and the underlying physical principles have been discussed. This paper clearly demonstrates that the photoelectric characteristics of the DBD reactor are significantly influenced by both the applied voltage and energy density, thus providing helpful insights into the energy evaluation and application of high-voltage discharges.