Production and photoexcited dynamics of reaction intermediates with photolyses of benzyl chloride (BzCl) and methyl-substituted benzyl chlorides (MeBzCls) were studied by using stepwise two-color laser excitation transient absorption (TC-TA) and two-color laser excitation time-resolved thermal lensing (TC-TRTL) measurements. With photoexcitation of BzCl the formation of transient photorearranged isomer was suggested in the previous paper [Res. Chem. Intermed. 2001, 27, 137]. Such an isomer formation for MeBzCls was also observed in a 248 nm excitation. It was found that further photoexcitation of the isomers with the 308 nm light caused photodissociation to yield the corresponding benzyl radicals. The reaction quantum yield and the molar absorptivity of the photorearranged isomer of BzCl were estimated. The heat of reaction for the photodissociation of the isomer was successfully determined with the TC-TRTL measurement. These experimental results were consistent with MO calculations.