Phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) film was deposited by a filtered cathodic vacuum arc technology with PH3 as the dopant source. The composition and structural characteristics were investigated by X-ray photoelectron spectroscope and Raman spectroscope, and the electrochemical behaviors of ta-C:P film were examined by cyclic voltammetry and differential pulse voltammetry. Results indicate that phosphorus implantation does not remarkably change the amorphous structure of the film but enhances the clustering of sp(2) sites dispersed in sp(3) skeleton and the evolution of structrual ordering. Ta-C:P film pretreated by acid exhibits a large electrochemical potential window and a low background current in H2SO4 solution, a considerable electrochemical activity toward Cl-, quick electrode response and a high signal for Cu2+ and Cd2+ analysis. These characteristics greatly demonstrate a potential application of conductive ta-C:P film as electrodes for analysis and treatment of trace metal ions in waste water.