Due to increasing gas prices and environmental concerns, battery propelled electric vehicles (BEVs) and hybrid electric vehicles (HEVs) have recently drawn more attention. In BEV and HEV configurations, the rechargeable energy storage system (RESS) is a key design issue [1–3]. Thus, the system should be able to have good performances in terms of energy density and power capabilities during acceleration and braking phases. However, the thermal stability, charge capabilities, life cycle and cost can be considered also as essential assessment parameters for RESS systems.Presently batteries are used as energy storage devices in most applications. These batteries should be sized to meet the energy and power requirements of the vehicle. Furthermore, the battery should have good life cycle performances. However, in many BEV applications the required power is the key factor for battery sizing, resulting in an over-dimensioned battery pack [4,5] and less optimal use of energy [4]. These shortcomings could be solved by combination of battery system with supercapacitors [6–8]. In [9], it is documented that such hybridization topologies can result into enhancing the battery performances by increasing its life cycle, rated capacity, reducing the energy losses and limiting the temperature rising inside the battery. Omar et al. concluded that these beneficial properties are due to the averaging of the power provided by the battery system [4,6,9]. However, the implementation of supercapacitors requires a bidirectional DC–DC converter, which is still expensive. Furthermore, such topologies need a well-defined energy flow controller (EFC). Price, volume and low rated voltage (2.5–3 V) hamper the combination of battery with supercapacitors [6,10]. In order to overcome these difficulties, Cooper et al. introduced the Ultra-Battery, which is a combination of lead-acid and supercapacitor in the same cell [11]. The new system encompasses a part asymmetric and part conventional negative plate. The proposed system allows to deliver and to absorb energy at very high current rates. The Ultra-Batteries have been tested successfully in the Honda Insight. However, this technology is still under development. In the last decade, a number of new lithium-ion battery chemistries have been proposed for vehicular applications. In [12–15], it is reported that the most relevant lithium-ion chemistries in vehicle applications are limited to lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium manganese spinel in the positive electrode and lithium titanate oxide (LTO) in the negative electrode. In this chapter, the performance and characteristics of various lithium-ion based batteries and supercapacitor will be evaluated and discussed. The evaluation will be mainly based on the electrical behavior. Then the characteristics of these RESS systems will be investigated based on the electrical and thermal models.