Degradation of Supercapacitors (SC) is quantified by accelerated ageing tests. Energy cycling tests and calendar life tests are used since they address the real operating modes. The periodic characterization is used to analyse evolution of the SC parameters as a whole, and its Helmholtz and diffusion capacitances. These parameters are determined before the ageing tests and during 3 × 105 cycles of both 75% and 100% energy cycling, respectively. Precise evaluation of the capacitance and Equivalent Series Resistance (ESR) is based on fitting the experimental data by an exponential function of voltage vs. time. The ESR increases linearly with the number (No) of cycles for both 75% and 100% energy cycling, whereas a super-linear increase of ESR vs. time of cycling is observed for the 100% energy cycling. A decrease of capacitance in time had been evaluated for 2000 hours of ageing of SC. A relative change of capacitance is ΔC/C0 = 16% for the 75% energy cycling test and ΔC/C0 = 20% for the 100% energy cycling test at temperature 25°C, while ΔC/C0 = 6% for the calendar test at temperature 22°C for a voltage bias V = 1.0 Vop. The energy cycling causes a greater decrease of capacitance in comparison with the calendar test; such results may be a consequence of increasing the temperature due to the Joule heat created in the SC structure. The charge/discharge current value is the same for both 75% and 100% energy cycling tests, so it is the Joule heat created on both the equivalent series resistance and time-dependent diffuse resistance that should be the source of degradation of the SC structure. The diffuse resistance reaches a value of up to 30Ω within each 75% energy cycle and up to about 43Ω within each 100% energy cycle.