Thin films of Al, and Co or Ni based Layered Double Hydroxides (LDH) have been electrochemically deposited on four different supports (Grafoil, Toray Carbon Paper, Carbon Cloth and Nickel Foam) through a potentiostatic or a potentiodynamic approach. The obtained films have been fully characterized to compare their properties in dependence on the different deposition techniques and substrates. Finally, the Grafoil support modified with a Ni /Al-LDH has been employed as cathode in combination with a Grafoil anode modified with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) also electrosynthesized, in order to develop an all-binder-free hybrid supercapacitor as a proof of concept to demonstrate the applicability in the field of energy storage.