A novel approach to analyze electrochemical impedance spectroscopy (EIS), based on evolutionary programming, has been utilized to characterize supercapacitors operation mechanism and degradation processes. This approach poses the ability of achieving a comprehensive study of supercapacitors via solely AC measurements. Commercial supercapacitors were examined during accelerated degradation. The microstructure of the electrode-electrolyte interface changes upon degradation; electrolyte parasitic reactions yield the formation of precipitates on the porous surface, which limit the access of the electrolyte ions to the active area and thus reduces performance. EIS analysis using Impedance Spectroscopy Genetic Programming (ISGP) technique enables identifying how the changing microstructure is affecting the operation mechanism of supercapacitors, in terms of each process effective capacitance and time constant. The most affected process is the transport of electrolyte ions at the porous electrode. Their access to the whole active area is hindered, which is shown in our analysis by the decrease of the capacitance gained in the transport and the longer time it takes to penetrate the entire pores depth. Early failure detection is also demonstrated, in a way not readily possible via conventional indicators. ISGP advanced analysis method has been verified using conventional and proven techniques: cyclic voltammetry and post mortem measurements.