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Polyaniline-based sensing electrodes were developed for potentiometric determination of ascorbic acid in solutions. Two different types of PANI-based sensors were constructed. These are PANI-covered screen-printed carbon electrode and electrically conducting PANI/nylon-6 composite film. The influence of electrode template on the analytical performance characteristics was investigated. Analytical conditions were selected in such a way so that PANI to be reduced by ascorbic acid but be unable to interact with dopamine. In such conditions, the presence of 0.4 mM dopamine does not interfere with ascorbic determination. Ascorbic acid detection limit was found to be as low as 4 µM.