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A gold electrode was firstly modified with the optimum self\u2010assembled monolayer (SAM), 1,6\u2010hexanedithiol, followed by the subsequent adsorption of gold nanoparticles (AuNPs) and, then, the monoclonal antibody to recognize PSA was immobilized. The influence of the most significant experimental variables (SAM type and incubation time, AuNPs deposition, antibody concentration and bovine serum albumin immobilization) on the biosensor response was studied by microscopy and voltammetry techniques. The electroanalytical detection was based on the interaction between PSA antibody and PSA <jats:italic>via<\/jats:italic> square\u2010wave voltammetry using ferrocyanide\/ferricyanide as electrochemical redox indicator. Using the proposed immunosensor, PSA was specifically detected within the linear range between 0.2 and 200\u2005ng\u2009mL<jats:sup>\u22121<\/jats:sup> with 0.01\u2005ng\u2009mL<jats:sup>\u22121<\/jats:sup> as limit of detection. 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