Tetrachloroethene reductive dehalogenase (PceA), a corrinoid-containing enzyme from Sulfurospirillum multivorans, is highly active for the sequential reduction of the organohalide tetrachloroethene (PCE) to trichloroethene (TCE), then regiospecifically to cis-1,2-dichloroethene (cDCE). We demonstrate direct electron transfer from graphite and semiconductor electrodes to PceA adsorbed onto the electrode surface. Colloidal TiO2 nanoparticles modified with PceA efficiently carry out the sequence of dehalogenation reactions under UV light irradiation.