We describe the voltammetric behavior of an anion-exchange membrane, hexamethyl-pterphenyl poly(benzimidazolium) (HMT-PMBI). The anion-exchange properties of HMT-PMBI chemically modified electrodes were investigated using K 4 Fe(CN) 6 and K 2 IrCl 6 as redox probes. The permselectivity properties of HMT-PMBI chemically modified electrodes were ascertained using tris(2-2')bipyridyl-ruthenium(II) chloride Ru(bpy) 3 2+ . Cyclic voltammetry and chronoamperometry were utilized to extract parameters such as the concentration of the redox mediators inside the films and the apparent diffusion coefficients. We found the concentration of K 4 Fe(CN) 6 and K 2 IrCl 6 redox species within HMT-PMBI-coated films to be on the order of 0.04-0.1 mol·dm −3 , and values of D app ca. 10 −10 -10 −9 cm 2 ·s −1 . To evaluate the possibility of using such a polymer coating in electroanalysis, HMT-PMBI-modified electrodes were utilized for the voltammetric detection of uric acid in artificial urine, Surine ® and ascorbic acid in Vitamin C samples. The results showed that HMT-PMBI-coated electrodes can detect uric acid in Surine ® with a limit of detection (LoD) of 7.7 µM, sensitivity of 0.14 µA·µM −1 ·cm −2 , and linear range between 5 µM and 200 µM, whereas for Vitamin C tablets, the LoD is 41.4 µM, the sensitivity is 0.08 µA·µM −1 ·cm −2 , and the linear range is between 25 µM and 450 µM.Sensors 2020, 20, 443 2 of 20 modification of electrode surfaces. Originally, ionomers were synthesized for fuel cell applications, and specifically used as membranes to separate the anode from the cathode compartments, due to their very good transport of opposite charge ions [8][9][10][11]. For instance, in proton exchange fuel cells (PEMFCs), the ionomer is made of a polymer having a net negative charge (typically sulfonic or carboxylic) that transports protons from the anode to the cathode, whereas in alkaline fuel cells (AFCs), the ionomer is made of a polymer with a net positive charge (typically ammonium or phosphonium) that transports hydroxide ions from the cathode to anode. These ion-exchange properties made ionomers suitable as membranes in water electrolyzers and desalination units [12][13][14]. From an electroanalytical point of view, ionomer-coated electrodes are particularly attractive due to their very good ion-exchange properties, which allow the preconcentration of analytes having opposite charge even at very low concentrations, at the same time providing protection against potential interferences and fouling. An example is Nafion ® , a cation exchange ionomer widely used for the determination of positively charged dopamine up to ultra-trace concentrations, whilst protecting the electrode from the potential interferences of ascorbic acid [15,16]. Instead, in the case of anion-exchange ionomers, the literature extensively reported ammonium functionalized ionomers [17][18][19][20][21]; more recently, we reported phosphonium-based ionomers [22,23]. These ionomers have also been extensively studied due to their charge transport mechanisms w...