In this paper, a simple dip-coating technique is used to deposit a poly (3-hexylthiophene) and [6, 6]-phenyl C61-butyric acid methyl ester (P3HT:PCBM)/nickel–aluminum-layered double hydroxide-graphene foam (NiAl-LDH-GF) composite onto a nickel foam (NF) serving as a current collector. A self-organization of the polymer chains is assumed on the Ni-foam grid network during the slow “dark” drying process in normal air. Electrochemical cyclic voltammetry (CV) and constant charge–discharge (CD) measurements show an improvement in the supercapacitive behavior of the pristine P3HT:PCBM by an order of magnitude from 0.29 F cm−2 (P3HT:PCBM nanostructures) to 1.22 F cm−2 (P3HT:PCBM/NiAl-LDH-GF composite structure) resulting from the addition of NiAl-LDH-GF material at a current density of 2 mA cm−2. This capacitance retention after cycling at 10 mA cm−2 also demonstrates the electrode material’s potential for supercapacitor applications.