Supercapacitors as novel energy storage devices between conventional capacitors and batteries, with more specific capacitance and energy densities than conventional capacitors and more power densities than batteries are to be used in many fields. And, social demand on fuel economy and reducing pollution needs equipment of new function such as energy storage system with good power performance, high cyclability and good energy efficiency. Supercapacitor is regarded as one of good alternatives for meeting the requirement of market with excellent power performance and high cyclability. This paper deals with the fundamental characteristics of supercapacitor unit and charge and discharge behavior of supercapacitor module for developing 42V hybrid energy storage system with lead acid battery and supercapacitor in order to adopt to 42V power net for vehicle.