The photodecomposition of coumarin-3-t-Bu peroxyester (1) and coumarin-3-carbonyl-m-chlorobenzoylperoxide (2) has been studied using nanosecond and femtosecond spectroscopy to elucidate the nature of transient species involved. Excitation of the cournarin chromophore leads to its singlet excited-state decaying with the rate 9 x 10(9) s(-1) that results from a composite of emission, intersystem crossing, thermal relaxation, and -O-O- bond homolysis. Dissociation of the weak oxygen-oxygen bond proceeds from both triplet and singlet excited states. The nature of this combination of states is predissociative rather than dissociative as demonstrated by the relatively slow rates of oxygen-oxygen bond rupture. The decomposition of 1 and 2 leads to the formation of coumarin-3-carbonyloxyl radical (R1). The later was observed spectroscopically on the nanosecond time scale using both time-resolved FTIR and UV-vis transient techniques. RI is consumed in two competitive processes: unimolecular decarboxylation and bi-molecular hydrogen atom transfer. The rates of these reactions are 4.3 x 10(5) s(-1) and 1 x 10(6) M-1 s(-1) respectively. The transition state geometries and energies of decarboxylation of RI have been determined using DFT calculations and are compared with values for the benzoyloxyl radical. The decarboxylation of RI proceeds via a transition state in which the carboxyl group is almost perpendicular (dihedral angle 114 degrees) to the plane of the cournarin chromophore. The transition state of the benzoyloxyl radical, in contrast, is flat (0 degrees). The varied transition state energies of the radicals (13.6 kcal/mol for cournarin carboxyl radical vs 8 kcal/mol for benzoyloxyl radical) correlate with different decarboxylation rates of these two species.