An all solid double layer capacitor was assembled by using poly(ethylene oxide)/poly(propylene glycol)-b-poly(ethylene glycol)-b-poly(propylene glycol)-bis(2-aminopropyl ether) blend (PEO-NPPP) and LiClO4 as polymer electrolyte layer and PEO-NPPP–carbon black (CB) as electrode film. High molecular weight PEO and the block copolymer NPPP with molecular mass of 2000Da were employed, which means that the design is safe from the point of view of solvent or plasticizer leakage and thus, a separator is not necessary. Highly conductive with large surface area nanostructured carbon black was dispersed in the polymer blend to produce the electrode composite. The electrolyte and electrode multilayers prepared by spray were studied by differential scanning calorimetry, atomic force microscopy (AFM) and impedance spectroscopy. The ionic conductivity as a function of temperature was fitted with the Williams–Landel–Ferry equation, which indicates a conductivity mechanism typical of solid polymer electrolyte. AFM images of the nanocomposite electrode showed carbon black particles of approximately 60nm in size well distributed in a semicrystalline and porous polymer blend coating. The solid double layer capacitor with 10wt.% CB was designed with final thickness of approximately 130μm and delivered a capacitance of 17Fg−1 with a cyclability of more than 1000 cycles. These characteristics make possible the construction of a miniature device in complete solid state which will avoid electrolyte leakage and present a performance superior to other similar electric double layer capacitors (EDLCs) presented in literature, as assessed in specific capacitance by total carbon mass.