De-excited dynamics of p-chlorotoluene and p-dichlorobenzene have been investigated by the femtosecond pump-probe method in a supersonic molecular beam. The yields of the parent ion and daughter ion are examined as a function of the delay time between the pump and probe laser pulses. The lifetime constants of excited p-chlorotoluene and p-dichlorobenzene are determined. Possible de-excitation mechanisms are suggested that the initially excited S-1 state is predissociative via the repulsive triplet state. The substituent effects of additional chlorine atom and methyl group are discussed. Moreover, for the first time, we observe a novel quantum beat oscillation in p-dichlorobenzene. (c) 2005 Elsevier B.V. All rights reserved.