An overlap of the absorption spectrum of the hypochlorite ion (OCl(-)) and the ultraviolet (UV) end of the solar emission spectrum implies that solar photons can probably initiate the UV/chlorine advanced oxidation process (AOP). The application of this solar process to water and wastewater treatment has been investigated in this study. At the bench-scale, the OCl(-) photolysis quantum yield at 303 nm (representative of the lower end of the solar UV region) and at concentrations from 0 to 4.23 mM was 0.87 ± 0.01. Also the hydroxyl radical yield factor (for an OCl(-) concentration of 1.13 mM) was 0.70 ± 0.02. Application of this process, at the bench-scale and under actual sunlight, led to methylene blue (MB) photobleaching and cyclohexanoic acid (CHA) photodegradation. For MB photobleaching, the OCl(-) concentration was the key factor causing an increase in the pseudo first-order rate constants. The MB photobleaching quantum yield was affected by the MB concentration, but not much by the OCl(-) concentration. For CHA photodegradation, an optimal OCl(-) concentration of 1.55 mM was obtained for a 0.23 mM CHA concentration, and a scavenger effect was observed when higher OCl(-) concentrations were applied. Quantum yields of 0.09 ± 0.01 and 0.89 ± 0.06 were found for CHA photodegradation and OCl(-) photolysis, respectively. In addition, based on the Air Mass 1.5 reference solar spectrum and experimental quantum yields, a theoretical calculation method was developed to estimate the initial rate for photoreactions under sunlight. The theoretical initial rates agreed well with the experimental rates for both MB photobleaching and CHA photodegradation.