A small-molecular model reaction was designed to probe the reversible addition–fragmentation chain transfer (RAFT) process. In this reaction, alkoxyamine releases radicals that react in situ with dithioester through the RAFT process, generating new radicals through the fragmentation of the intermediate radical. The new radicals can be trapped by free 2,2,6,6-tetramethyl-piperidinyl-N-oxyl radicals (TEMPO) from homolysis of alkoxyamine. The overall reaction is the crossover of the leaving groups between alkoxyamine and dithioester. The advantage of this model as a probe of the RAFT process is that it does not involve polymerization-related elementary reactions such as initiation, propagation, and chain length dependent termination. The kinetics of the model reaction were measured using high-performance liquid chromatography, and then fitted by Monte Carlo simulation to estimate rate coefficients. The obtained rate coefficients of addition for various dithioesters fell into a narrow range of 107–108 L mol–1 s–1, whereas the rate coefficient of fragmentation was model-dependent. It was also found that a significant fraction of the dithioester was consumed by an unspecified additional mechanism. A tentative explanation is proposed in which the intermediate radical undergoes a secondary RAFT reaction with dithioesters, forming a secondary intermediate that serves as a radical reservoir.