Pt electrodes of different sizes (2 × 10−5−2 × 10−2 cm2) and geometries (disks and cylinders) were coated with the ultrathin non-conducting form of poly(o-phenylenediamine), PPD, using amperometric electrosynthesis. Analysis of the ascorbic acid (AA) and H2O2 apparent permeabilities for these Pt/PPD sensors revealed that the PPD deposited near the electrode insulation (Teflon or glass edge) was not as effective as the bulk surface PPD for blocking AA access to the Pt substrate. This discovery impacts on the design of implantable biosensors where electrodeposited polymers, such as PPD, are commonly used as the permselective barrier to block electroactive interference by reducing agents present in the target medium. The undesirable “edge effect” was particularly marked for small disk electrodes which have a high edge density (ratio of PPD-insulation edge length to electrode area), but was essentially absent for cylinder electrodes with a length of >0.2 mm. Sample biosensors, with a configuration based on these findings (25 μm diameter Pt fiber cylinders) and designed for brain neurotransmitter l-glutamate, behaved well in vitro in terms of Glu sensitivity and AA blocking.