Benzhydryl radicals and cations are reactive intermediates central to the under-standing of organic reactivity. They can be generated from benzhydryl halides by UV irradi-ation. We performed transient absorption (TA) measurements over the range from femto -seconds to microseconds to unravel the complete reaction scheme. The 290–720-nm proberange allows the unambiguous monitoring of all fragments. The appearance of the radical isdelayed to the optical excitation, the onset of the cation signal is found even later. Ab initiocalculations show that this non-rate behavior in the 100 fs range is due to wavepacket motionfrom the Franck–Condon region to two distinct conical intersections. The rise of the opticalsignal with a quasi-exponential time of 300 fs is assigned to the planarization and solvationof the photoproducts. The bond cleavage predominantly generates radical pairs. A subse-quent electron transfer (ET) transforms radical pairs into ion pairs. Due to the broad inter-radical distance distribution and the distance dependence, the ET is strongly non-exponen-tial. Part of the ion pairs recombine geminately. The ET and the recombination are terminatedby the depletion of close pairs and diffusional separation. The remaining free radicals and cations undergo further reactions in the nanosecond to microsecond regime.