An Immunosensor for the detection of polychlorinated biphenyls (PCB) has been developed, using carbon-based screen-printed electrodes as solid-phase and signal transducers. The immunosensor realised is based on a direct competitive immunoassay scheme, in which the antibody against PCB was directly immobilised onto the carbon surface of the screen-printed electrode. Competition between the PCBs present in the sample and a fixed concentration of an enzyme-labelled congener was realised and evaluated by electrochemical detection. The immunosensor developed was tested on Arochlor mixtures (1242 and 1248), and was applied in environmental and food analysis by testing some real samples (from animal tissues and marine sediments). Results obtained demonstrate the ability of this device to detect PCBs in complex matrices.