The almost instantaneous production of radicals via laser pulse initiation during RAFT polymerization in conjunction with measuring the subsequent decay of the intermediate RAFT radical concentration by μs time-resolved ESR spectroscopy allows for deducing addition and fragmentation rate coefficients of the RAFT process. By tracing monomer concentration via μs time-resolved NIR spectroscopy after an initiating laser pulse during RAFT polymerization, the rate coefficient of termination between propagating radicals and its chain-length dependence may be assessed. Results obtained by the novel SP-PLP-ESR-RAFT and SP-PLP-NIR-RAFT techniques are presented for butyl acrylate polymerization.