Electrocatalysis, especially in cascade enzymatic systems, is often hindered by inefficient electron transfer between sequential enzymes. To overcome this challenge, we developed a strategy that integrates metal–phenolic networks (MPNs) with enzymatic catalysis. This was achieved by combining naturally occurring polyphenols—tannic acid, gallic acid, and lignin—with transition metal ions like copper, cobalt, and iron, forming functional coatings on electrode surfaces. Using electropolymerization on screen-printed electrodes, we established stable MPN layers capable of encapsulating and supporting electrochemical enzymatic reactions. Glucose oxidase and horseradish peroxidase were employed as model enzymes for their complementary redox properties, forming an interconnected catalytic cycle. We systematically evaluated the performance of these enzyme cascades across various MPN compositions to identify the most effective combinations for enhancing bioelectrocatalytic activity. This platform offers a promising approach to improving electron transfer efficiency in biosensing and biofuel cell technologies.