Coating microvoltammetric electrodes with a poly(ester‐sulfonic acid) film offers substantial improvements in their selectivity toward cationic neurotransmitters. This charged film tends to exclude anionic interferences, such as ascorbic acid or anionic biogenic amine metabolites. The temporal response of polyester‐ionomer‐coated microelectrodes is evaluated under dynamic flow‐injection conditions. Chro‐noamperometry and cyclic voltammetry are used to explore the discriminative properties of these microelectrodes under quiescent conditions. The attractive permselective, ion‐exchange, antifouling, and dynamic properties of the polyester ionomer, coupled with its low cost and strong adherence to surfaces, could be very valuable for in vivo brain electrochemistry. Copyright © 1990 VCH Publishers, Inc.