Rutile TiO2 nanorod (TiNR) arrays were fabricated on a boron-doped diamond (BDD) substrate by a simple hydrothermal synthesis method. A fluorine-doped tin oxide (FTO) electrode grown with TiNR arrays was also prepared using the same technology for comparison. Field-emission scanning electron microscopy results show that oriented TiNR arrays can grow vertically on the surface of BDD and FTO electrodes. TiNR arrays grown on both electrodes had the same length (3 μm). In comparison with the TiNR/FTO electrode, the TiNR/BDD electrode demonstrated a higher photoelectrocatalytic activity for the degradation of water and organic compounds, which is mostly attributed to the formation of a p-n heterojunction between the TiNR arrays and BDD at high potential, apart from the density of TiNR. A linear relationship between the photoelectrocatalytic current and the organic concentration can be observed on both electrodes. However, the linear range between net photoelectrocatalytic current values and organic compound concentrations for the TiNR/BDD electrode are much greater than those for the TiNR/FTO electrode, which makes the TiNR/BDD electrode a versatile material for the photocatalytic degradation and sensing of organic compounds.