High-performance devices based on conducting polymers (CPs) require the fabrication of a thick CP-coated electrode with high stability. Herein, we propose a method for enhancing the interfacial adhesion strength between a gold electrode and an electropolymerized polypyrrole (pPy) layer by introducing a polyethyleneimine (PEI) layer. Although this insulating layer hinders the initial growth of the pPy layer on the Au surface, it improves the adhesion by up to 250%. Therefore, a thick layer of pPy can be fabricated without delamination during drying. X-ray photoelectron spectroscopy shows that the PEI layer interacts with the Au surface via polar/ionic groups and van der Waals interactions. Scanning electron microscopy reveals that the cohesion of the pPy layer is stronger than the interfacial adhesion between the PEI layer and the pPy layer. Importantly, the electroactivities of pPy and its dopant are unaffected by the PEI layer, and the electrochemical storage capacity of the pPy layers on the PEI-coated Au electrodes increases with thickness, reaching ~530 mC/cm2. Negative potential sweep is detrimental to pPy layer adhesion: pPy layers on a bare Au electrode peel off instantly as the potential is swept from 0.2 to -0.7 V, and most of the charge stored in the layer becomes inaccessible. In contrast, pPy layers deposited on PEI coated Au electrode are mechanically stable and majority of the charge can be accessed, demonstrating that this method is also effective for enhancing electrochemical stability. Our simple approach can find utility in various applications involving CP-coated electrodes, where thickness-dependent performance must be improved without loss of stability.