The propagation and termination rate coefficients for bulk polymerization of the butyl acrylate dimer (BA dimer) are determined by pulsed laser techniques. The rate coefficient for propagation, k p , is deduced for temperatures from 20 to 90°C via the pulsed laser polymerization–size exclusion chromatography (PLP–SEC) method at pulse repetition rates between 1 and 10Hz. The Arrhenius parameters were found to be: E A (k p )=(34.2±1.0)kJmol −1 and A(k p )/Lmol −1 s −1 =(1.08±0.49)×10 7 Lmol −1 s −1 . The termination rate coefficient, k t , has been measured via SP-PLP–ESR, single pulse-pulsed laser polymerization in conjunction with time-resolved electron spin resonance detection of radical concentration. The resulting Arrhenius parameters as deduced from the temperature range −15 to +30°C are: E A (〈k t 〉)=(22.8±3.7)kJmol −1 and log(A/Lmol −1 s −1 )=10.6±1. The chain-length dependence of k t was studied at 30°C. For short chains a significant dependence was found which may be represented by an exponent α=0.79 in the power-law expression k t (i)=k t 0 i −α .