For electric vehicles, a supercapacitor can be coupled to the electrical system in order to increase and optimize the energy and power densities of the drive system during acceleration and regenerative breaking. This study looked at the charge acceptance and maximum discharge ability of a valve regulated lead acid (VRLA) and a Li-ion battery connected in parallel to supercapacitors. The test procedure evaluated the advantage of using a supercapacitor at a 2 F:1 Ah ratio with the battery types at various states of charge (SoC). The results showed that about 7% of extra charge was achieved over a 5-s test time for a Li-ion hybrid system at 20% SoC, whereas at the 80% SoC the additional capacity was approximately 16%. While for the VRLA battery hybrid system, an additional charge of up to 20% was achieved when the battery was at 80% SoC, with little or no benefit at the 20% SoC. The advantage of the supercapacitor in parallel with a VRLA battery was noticeable on its discharge ability, where significant extra capacity was achieved for short periods of time for a battery at the 60% and 40% SoC when compared to the Li-ion hybrid system. The study also made use of Electrochemical Impedance Spectroscopy (EIS) with a suitable equivalent circuit model to explain, in particular, the internal resistance and capacitance differences observed between the different battery chemistries with and without a supercapacitor.