This study has demonstrated that the local chemical environment is distinctly different when highly active enzymes are confined at high loading under electrocatalytic conditions. This highlights the importance of distinguishing electrochemical techniques into two groups. Firstly, those which easily allow for mechanistic and fundamental enzyme studies, such as the use of unconfined, flat rotating disk electrodes which minimise mass transport effects and prevent the establishment of local environments. And secondly, stationary, porous electrodes which allow for significantly higher loading and current densities for product application purposes, but also establish local chemical environments distinct from the bulk solution. Whilst high loading porous electrodes can be used in enzymology studies, the local environment changes must be accounted for to prevent misinterpretation of activity changes. A FEM has been shown to be a powerful technique for understanding fundamental experimental observations in highly complex and convoluted applications. This research prompts a variety of other implications not specifically addressed here, but of equal importance to the field, including the local concentration of salt species and electron mediators, the confinement effect of redox polymers, the local pH decrease in oxidation reactions, and local pH changes in live cell biofilms. Supporting Information.