River waters in China have dual contamination by nutrients and recalcitrant organic compounds. In principle, the organic compounds could be used to drive denitrification of nitrate, thus arresting eutrophication potential, if the recalcitrant organics could be made bioavailable. This study investigated the potential to make the recalcitrant organics bioavailable through photocatalysis. Batch denitrification tests in a biofilm reactor demonstrated that dual-contaminated river water was short of available electron donor, which resulted in low total nitrogen (TN) removal by denitrification. However, the denitrification rate was increased significantly by adding glucose or by making the organic matters of the river water more bioavailable through photocatalysis. Photocatalysis for 15 min increased the Chemical Oxygen Demand (COD) of the river water from 53 to 84 mg·L and led to a 4-fold increase in TN removal. The increase in TN removal gave the same effect as adding 92 mg·L of glucose. During the photocatalysis experiments, the COD increased because photocatalysis transformed organic molecules from those that are resistant to dichromate oxidation in the COD test to those that can be oxidized by dichromate. This phenomenon was verified by testing photocatalysis of pyridine added to the river water. These findings point to the potential for N removal via denitrification after photocatalysis, and they also suggest that the rivers in China may be far more polluted than indicated by COD assays.