Electrodes with nanosheet architectures can offer the possibility to achieve enhanced energy storage performance. Herein, we have designed and synthesized novel nanosheet structures of CoAl layered double hydroxide (LDH)-polyaniline (PANI) nanocomposite thin films by a hydrothermal-electrodeposition method. The molecular structure, crystal structure, morphology and chemical composition of the composites were characterized by FT-IR, XRD (SXRD), FESEM, and XPS, whereas their electrochemical properties were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge tests. Compared with the unmodified CoAl LDH, the CoAl LDH-PANI exhibits significantly improved the specific capacitance and cyclic stability. The composite exhibits a high specific capacitance of 528 F/g at a current density of 10 A/g and excellent cyclic stability with an increase of the specific capacitance of 42.7% after 6000 cycle tests. We revealed the degradation behavior of PANI in 1 M KOH/KCl electrolyte, and the active degradation products also further increased the total specific capacitance of the composite. The enhanced electrochemical performance of the nanocomposite can be attributed to its well-designed nanostructure and the synergistic effects of each component. By analyzing the band structure and density of states of CoAl LDH and PANI, we proposed the possible mechanism of synergistic effect in a new perspective.