Nanosecond time-resolved absorption and Raman spectra of carbazole (CzH) and N-ethylcarbazole (CzEt) in acetonitrile revealed that photo-deprotonation and photoionization of carbazole occurred through different biphotonic processes on excitation with 308 nm light. The photo-deprotonation to produce carbazyl radical (Czz) by the homolytic cleavage of the N -H bond proceeded through the T 1 state, while the photoionization to generate cation radical (CzH ΓΎz ) occurred in the singlet manifold through the S 1 state. In nonpolar cyclohexane, CzH ΓΎz was not detected. It was not possible, however, to determine whether the two photon-energy of 308 nm light is not sufficiently large to overcome the ionization energy of CzH in cyclohexane, or the lifetime of CzH ΓΎz is too short in nonpolar cyclohexane to be detected in the nanosecond time domain. Neither Czz nor CzH ΓΎz was observed in the picosecond time domain due to small energy and short width of the picosecond laser pulse for biphotonic excitation. Monophotonic ionization of CzH did not occur with 293 nm light. No indication was obtained which suggested the deviation from the planarity of the S 0 structure for all the transients. Softening of the phenyl rings was found to occur on going from S 0 to the transients in the increasing order, S 1 , Czz and T 1 :