A simple electrical model has been established to describe supercapacitor behaviour as a function of frequency, voltage and temperature for hybrid vehicle applications. The electrical model consists of 14 RLC elements, which have been determined from experimental data using electrochemical impedance spectroscopy (EIS) applied on a commercial supercapacitor. The frequency analysis has been extended for the first time to the millihertz range to take into account the leakage current and the charge redistribution on the electrode. Simulation and experimental results of supercapacitor charge and discharge have been compared and analysed. A good correlation between the model and the EIS results has been demonstrated from 1mHz to 1kHz, from −20 to 60°C and from 0 to 2.5V.