Resonance Raman (RR) spectra and quantum chemical calculations were used to investigate the photodissociation dynamics of propanil in the S2 state. The RR spectra indicate that the photorelaxation dynamics for the S0 → S2 excited state of propanil is predominantly along nine motions: C═O stretch, ν51 (1659 cm(-1)), ring C═C stretch, ν50 (1590 cm(-1)), NH wag/ring C═C stretch, ν49 (1534 cm(-1)), ring CCH in-plane bend/NH wag, ν42 (1383 cm(-1)), NH wag/-CH2- rock, ν41 (1353 cm(-1)), ring C═C stretch/NH wag/-CH2- rock in-plane, ν40 (1299 cm(-1)), Ph-NH stretch/ring CCH in-plane bend, ν37 (1236 cm(-1)), ring CCH in-plane bend, ν35 (1150 cm(-1)), -CH2CH3 twist, ν33 (1080 cm(-1)), ring trigonal bend, ν31 (1029 cm(-1)), ring CCH bend out-of-plane, ν27 (899 cm(-1)), whole skeleton deformation in-plane, ν20(688 cm(-1)). Strong electron coupling between S1 and S2 of propanil is found by quantum chemistry calculations and depolarization spectra. The excited-state dynamics of the S2 state is discussed, and the results are compared with the previously reported results for formanilide to examine the Cl substitution effect.