The single pulse pulsed laser polymerization electron paramagnetic resonance (SP-PLP-EPR) method affords the detailed kinetic analysis of acrylamide polymerization in aqueous solution. Highly time-resolved SP-PLP-EPR experiments for 10 and 20 wt % AAm were first carried out at -5 degrees C, where only secondary propagating radicals (SPRs) occur. In a second step, the time evolution of midchain radicals (MCRs), produced from SPRs by backbiting, was measured at higher temperatures. The termination kinetics, including chain-length dependent termination of SPRs, the backbiting rate of SPRs, and the propagation rate of MCRs were determined. The rate coefficients from SP PLP-EPR in conjunction with the known propagation rate coefficient of SPRs, enable the simulation of the kinetics and product properties of AAm radical polymerizations in aqueous solution.