AbstractGlassy carbon electrodes modified with coatings of poly‐[1‐methyl‐3‐(pyrrol‐1‐ylmethyl)pyridinium], poly‐MPP, were prepared by electrochemical oxidation of the suitable monomer in acetonitrile solutions. The anion exchange properties of the coated electrode were exploited in aqueous solutions for preconcentrating and detecting the anionic complex HgCl42−, which is the prevailing inorganic HgII species in seawater and other chloride media. The partition coefficients for the ion‐exchange equilibrium involved were calculated from voltammetric data and compared with those obtained at electrodes coated with Tosflex, a perfluorinated anion exchanger, and poly(vinylpyridine). The selectivity of the poly‐MPP coated electrodes towards the rejection of copper interference was also studied. The optimization of experimental conditions allowed the development of a differential pulse voltammetric method for the determination of submicromolar mercury concentrations with a detection limit of 0.1 nM. The method was applied to the analysis of mercury in the pore‐waters of tidal sediments of the Lagoon of Venice (Italy), determining HgII concentration values in the 70–80 nM range.