Linear sulphonated poly(arylethersulphone) (SPAES) membranes were tested and compared with Nafion, as electrode modifiers for electroanalytical purposes. Different preparation parameters were evaluated: casting solvent, method of drying and storage, polymer ionic moieties counter-ion. In particular, the casting solvent seems to play a key role in the final modified electrode performances. Four solvents characterized by different boiling point and polarity were tested: dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP). The best electrode, particularly in terms of highest peak currents, was the one prepared using a 1% m/v solution of polymer in NMP, dried at 25 °C in a drying oven. Its performances are explained in terms of a favourable membrane organization enabling a thin layer diffusion and/or a preconcentration mechanism.