Titanium dioxide (TiO(2)) and boron-doped diamond (BDD) are two of the most popular functional materials in recent years. In this work, TiO(2) nanoparticles were immobilized onto the BDD electrodes by a dip-coating technique. Continuous and uniform mixed-phase (anatase and rutile) and pure-anatase TiO(2)/BDD electrodes were obtained after calcination processes at 700 and 450 degrees C, respectively. The particle sizes of both types of TiO(2) film range from 20 to 30 nm. In comparison with a TiO(2)/indium tin oxide (ITO) electrode, the TiO(2)/BDD electrode demonstrates a higher photoelectrocatalytic activity toward the oxidation of organic compounds, such as glucose and potassium hydrogen phthalate. Among all the tested TiO(2) electrodes, the mixed-phase TiO(2)/BDD electrode demonstrated the highest photoelectrocatalytic activity, which can be attributed to the formation of the p-n heterojunction between TiO(2) and BDD. The electrode was subsequently used to detect a wide spectrum of organic compounds in aqueous solution using a steady-state current method. An excellent linear relationship between the steady-state photocurrents and equivalent organic concentrations was attained. The steady-state oxidation photocurrents of the mixed-phase TiO(2)/BDD electrode were insensitive to pH in the range of pH 2-10. Furthermore, the electrodes exhibited excellent robustness under strong acidic conditions that the TiO(2)/ITO electrodes cannot stand. These characteristics bestow the mixed-phase TiO(2)/BDD electrode to be a versatile material for the sensing of organic compounds.