An overoxidized poly(3,4-ethylenedioxythiophene) film-modified screen-printed carbon electrodes (SPCE/PEDOTox) was prepared and characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and water contact angle techniques. The obtained film is a porous structure with highly abundant oxygen functionality. The SPCE/PEDOTox could adsorb cations strongly and perform catalytic oxidation of biomolecules. The potential-induced adsorption of dopamine was observed for SPCE/PEDOTox. A simple medium-exchange procedure was developed for the selective determination of dopamine by the use of the dopamine-adsorbed electrode. Under optimal differential pulse voltammetry (DPV), the proposed assay can be employed in the determination of submicromolar concentration of dopamine without the coexisting interferences of ascorbic acid (1000-fold) and uric acid (10-fold).