For the previously developed radiation-induced oxidation mediated by organochlorides, we found that the yield of the organochloro peroxyl radical intermediate depends on the concentrations of organochloride and molecular oxygen. To investigate this dependency and determine the optimal ratio, we developed a reaction network and constructed a mathematical model that incorporates the key reactions within the network. We used the model to calculate the yields of peroxyl radical at various concentrations of oxygen and organochloride. Experimental detection of the peroxyl radical using a thioether as probe demonstrated similar yields and trends as the simulated results, corroborating the proposed network. Camptothecin was caged by a thioether derivate to test the viability of using thioether as a radiation sensitive group. The oxidation of thioether by irradiating aqueous solutions containing organochloride showed high uncaging yields. The results indicate the thioether cage is a promising radiation sensitive group.