For the fabrication of thin films, Physical Vapor Deposition (PVD) techniques specified greater contribution than all other deposition techniques. Laser Ablation or Pulsed Laser deposition (PLD) technique is the one of most promising techniques for the fabrication of thin films among all other physical vapor deposition. In particular, flexible thin-film energy storage fabrication PLD plays an important role due to its special parameters such as fine thickness control, partial pressure atmospheric condition, pulsed repetition rate, in-situ annealing and microstructure optimization. Very recently, thin film supercapbatteries have been broadly studied, in which the battery and supercapacitor based electrodes are combined to obtain a high specific power and specific energy density and extended cycle stability. In order to fabricate thin film supercapbatteries, electrodes that have a large potential window, high capacitance, and capacity performance are vastly desired. Thus, the presented chapter represents an important enhancement in the growth of economical and eco-friendly thin flexible supercapbatteries and confirms their potential in sensible applications such as transport electronics devices and other gadgets.