A water-insoluble Polymer with Intrinsic Microporosity (or PIM, here for the particular case of the Tröger Base system PIM-EA-TB, BET area ca. 103 m2 -1g) is demonstrated to act as a rigid host environment for highly water-insoluble molecular catalysts, here tetraphenylporphyrinato-iron (FeTPP), surrounded by aqueous solution-filled micropores. A PIM-EA-TB film containing catalyst is deposited onto the electrode and immersed for voltammetry (i) with 4-(3-phenyl-propyl)-pyridine to give an organogel, or (ii) bare directly into aqueous solution. The porous host allows processes to be optimised as a function of solution phase, composition, and catalyst loading. Effective electron transfer as well as effective electrocatalysis is reported for aqueous oxygen and peroxide reduction. Given the use of completely water-insoluble catalyst systems, the methodology offers potential for application with a wide range of hitherto unexplored molecular electrocatalysts and catalyst combinations in aqueous media.