The ultrafast dynamics of benzaldehyde upon 260, 271, 284, and 287 nm excitations have been studied by femtosecond pump-probe time-of-flight mass spectrometry. A bi-exponential decay component model was applied to fit the transient profiles of benzaldehyde ions and fragment ions. At the S 2 origin, the first decay of the component was attributed to the internal conversion to the high vibrational levels of S 1 state. Lifetimes of the first component decreased with increasing vibrational energy, due to the influence of high density of the vibrational levels. The second decay was assigned to the vibrational relaxation of the S 1 whose lifetime was about 600 fs. Upon 287 nm excitation, the first decay became ultrashort (∼56 fs) which was taken for the intersystem cross from S 1 to T 2 , while the second decay component was attributed to the vibrational relaxation. The pump-probe transient of fragment was also studied with the different probe intensity at 284 nm pump.