The light-induced (266 nm) ultrafast decarboxylation of two peroxides R-1-C(O)O-OR2, with R-1 = phenyl and R-2 = benzoyl or tert-butyl, in solution has been studied on the picosecond time scale by absorption spectroscopy with a time resolution typically of 100 to 200 fs. The reaction was investigated in various solvents of different polarity and viscosity to elucidate the influence of the solvent environment on the decarboxylation rate. Transient intermediate benzoyloxy radicals, R-1-CO2, were monitored at wavelengths between 300 and 1000 nm. While the primary dissociation of the peroxide is too fast to be resolved, the dissociation of intermediate benzoyloxy radicals is clearly detected on the picosecond time scale. The mechanism of light-induced two-step dissociation is discussed, as is the dependence of reaction dynamics on the type of substituent R-2 as well as the branching ratio between prompt and delayed CO2 formation. A model for the decarboxylation process is presented that is based on molecular structure parameters and energies. The latter quantities, which are obtained from density functional theory calculations, serve as input data for calculations of the specific decomposition rate coefficients of benzoyloxy intermediates via statistical unimolecular rate theory. The predicted benzoyloxy radical decay data are compared with corresponding experimental concentration versus time traces.