Mass-selected resonant two-photon ionization (R2PI) and UV-UV hole-burning, and infrared-dip spectra of 5-cyanoindole (5CI) and its water clusters, 5CI-(H2O)(n) (n =1 and 2) were measured. Although, the structures of 5CI-(H2O)(1-2) are similar to those of 3CI-(H2O)1-2, the photofragmentation behaviors of the two systems are quite different due to the L-a-L-b state energy lowering and higher binding energies of 5CI-(H2O)(1-2) compared to those of 3CI-(H2O)(1-2). Especially for the case of 50-(I-120)2 cluster, shortening excited-state lifetime of 5CI-(H2O)(2) causes the broad background in the R2PI spectrum of 5CI-(H2O)(2). (C) 2016 Elsevier B.V. All rights reserved.