This article presents the results of the analysis of energy distribution of optical radiation emitted by electrical discharges in insulating liquids, such as synthetic ester, natural ester, and mineral oil. The measurements of optical radiation were carried out on a system of needle–needle type electrodes and on a system for surface discharges, which were immersed in brand new insulating liquids. Optical radiation was recorded using optical spectrophotometry method. On the basis of the obtained results, potential possibilities of using the analysis of the energy distribution of optical radiation as an additional descriptor for the recognition of individual sources of electric discharges were indicated. The results can also be used in the design of various types of detectors, as well as high-voltage diagnostic systems and arc protection systems.