In Power Systems, Synchronous Generators (SGs) are mostly used for generating electricity. Their insulation system, of which epoxy resin is a core component, plays a significant role in reliable operation. Epoxy resin has high mechanical strength, a characteristic that makes it a very good material for reliable SG insulation. Partial Discharges (PDs) are a constant threat to this insulation since they cause deterioration and consequential degradation of the aforementioned material. Therefore, it is very important to detect PDs, as they are both a symptom of insulation deterioration and a means to identify possible faults. Offline and Online PDs Tests are described, and a MATLAB/Simulink model, which simulates the capacitive model of PDs, is presented in this paper. Moreover, experiments are carried out in order to examine how the flashover voltage of epoxy resin samples is affected by different humidity levels. The main purpose of this manuscript is to investigate factors, such as the applied voltage, number, and volume of water droplets and water conductivity, which affect the condition of epoxy resin, and how these are related to PDs and flashover voltages, which may appear also in electrical machines’ insulation. The aforementioned factors may affect the epoxy resin, resulting in an increase in PDs, which in turn increases the overall Electrical Rotating Machines (EMs) risk factor.