This paper studies the effect of photosensitizer (acetone, H2O2, surfactant and pigment) on photodegradation of diclofenac (DCF) under simulated sunlight. The results demonstrate that degradation pathways proceed via pseudo first-order kinetics in all cases. The photodegradation rate was found to increase with increasing acetone and H2O2. Surfactant and pigment inhibited the photodegradation of DCF. Finally, four kinds of main degradation products were observed by high performance liquid chromatography/mass spectrometry and their chemical structures were suggested.