Photo-differential scanning calorimetry (photo-DSC) was used to investigate the photocuring kinetics of visible light initiated cationic photopolymerization of triethylene glycol divinyl ether (TEGDVE) with a diphenyl iodonium salt initiator and the three photosensitizers: 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTXO), camphorquinone (CQ), and acridine orange (AO). The effects of water, a tertiary amine, and a radical scavenger were used to probe the photocuring mechanism. The rate of photopolymerization was approximately proportional to the incident light intensity, and in each system, the final conversions, as measured by photo-DSC, also increased with raised incident light intensity. The power-law dependence of the reaction rate on the concentration of iodonium salt with CPTXO and AO was similar to 1.5, while the order is nearly unity with CQ as the photosensitizer, suggesting that these photosensitizers do not follow the same sensitization mechanism. For the three photosensitizers, the final conversions all increased with higher iodonium salt concentrations. After cessation of irradiation, a dark reaction was observed-although the rate of this process decreased rapidly with time (as shown by photo-DSC), the polymerization continued very slowly over a long period of time.