The kinetics of both the ions and radicals formed upon photolysis of diphenylmethyl chloride, (4-methoxyphenyl )phenylmethyl chloride, and bis(4-methoxyphenyl) methyl chloride in acetonitrile and propionitrile are examined by picosecond pump-probe spectroscopy. Both radical pairs and ion pairs are formed directly from a common excited state. In addition, the geminate radical pair decays by electron transfer to form either the contact ion pair or a covalent bond, as well as undergoes diffusional separation to free radicals.