Photodissociation of dichloromethane excited to the second C-H stretch overtone was performed by similar to235 nm photons that also tagged the Cl P-2(3/2) [Cl] and spin-orbit excited Cl P-2(1/2) [Cl*] photofragments via resonantly enhanced multiphoton ionization. The measured time-of-flight profiles together with the determined Cl*/Cl branching ratio suggest fast dissociation and involvement of several upper states of different symmetries mixing via curve crossing to release both Cl and Cl*. The determined ratio is higher than that obtained previously in the direct, almost isoenergetic, photodissociation of CH2Cl2 implying higher non-adiabaticity for vibrationally excited than for vibrationless ground state molecules. (C) 2003 Elsevier B.V. All rights reserved.