Polymers of intrinsic microporosity (or PIMs) provide porous materials due to their highly contorted and rigid macromolecular structures, which prevent space-efficient packing. PIMs are readily dissolved in solvents and can be cast into robust microporous coatings and membranes. With a typical micropore size range of around 1 nm and a typical surface area of 700-1000 m2 g-1, PIMs offer channels for ion/molecular transport and pores for gaseous species, solids, and liquids to coexist. Electrode surfaces are readily modified with coatings or composite films to provide interfaces for solid|solid|liquid or solid|liquid|liquid or solid|liquid|gas multiphase electrode processes.