A step forward in the understanding of rubber vulcanization with organic peroxides is provided by combining a proper arrangement between polymer, vulcanizing agent and cure conditions. For this purpose, an ethylene–vinyl acetate copolymer with a high content of vinyl acetate (70 mol%) was used since a fully saturated polymer backbone allows its vulcanization via peroxide. For the range of conditions analysed here, it is shown that the predominant process taking place is crosslinking via radical recombination, minimizing or even avoiding undesirable secondary reactions such us polymer degradation. Once conditions had been optimized, peroxide vulcanization was analysed in more depth in the presence of 2,2,6,6-tetramethylpiperidinyloxyl, which is a mediating stable free radical commonly used in controlled radical polymerization. Consequently, it was possible to differentiate the termination reaction from the initiation and propagation steps, allowing the determination of the enthalpy of formed C–C crosslinks as measured using calorimetry. It was possible to isolate and determine the contribution of the crosslinking pathway from the global vulcanization reaction by means of calorimetric methods at optimum conditions. In fact, this simple methodology could be an important tool for understanding in detail the complex peroxide vulcanization of elastomers since reactions involved in this process determine the final network structure, and thus the final elastic properties of these compounds.