Around 100 porphyrin units have been selectively linked at C(6)-O to a cellulose (Avicel). The properties of the metal-free and zincated porphyrin-celluloses 2 and Zn-2 have been determined by optical and electrochemical methods. Circular dichroism indicates a helical arrangement of the porphyrin units and reveals intra-chain coupling reminiscent, in the broadest sense, of strands of nucleic acids. Cyclic voltammetry and spectroelectrochemistry have been used to characterize the radical ions and dianions. The electrochromism of the oxidation of cellulose 2 to porphyrin radical cations of 2 has been employed for both molecular switching and the transduction of an electrochemical input into chiroptical signal expression.