The photodissociation dynamics of 2-iodotoluene following excitation at 266 nm have been investigated employing femtosecond time-resolved mass spectrometry.The photofragments are detected by multiphoton ionization using an intense laser field centered at 800 nm.A dissociation time of 380 ±50 fs was measured from the rising time of the co-fragments of toluene radical (C7H7) and iodine atom(I), which is attributed to the averaged time needed for the C-I bond breaking for the simultaneously excited nσ* and ππ* states by 266 nm pump light.In Addition, a probe light centered at 298.23 nm corresponding to resonance wavelength of ground-state iodine atom is used to selectively ionize ground-state iodine atoms generated from the dissociation of initially populated nσ* and ππ* states.And a rise time of 400 ± 50 fs is extracted from the fitting of time-dependent I+ transient, which is agreement with the dissociation time obtained by muitiphoton ionization with 800 nm.