The influence of water solvation on the photophysics of the indole chromophore has been investigated by revisiting the ultrafast relaxation of indole-water clusters. The dynamics after excitation in the 284-234 nm energy range has been tracked by time delayed ionization with a 1305 nm probe. The results collected in the indole-(H2O)(1)(+) mass channel, which were ascribed mainly to the indole-(H2O)(2)(+) cluster fragmented by dissociative ionization, reflect a dynamical behavior analogous to that observed for the isolated indole molecule. The two femtosecond time constants observed in the transients were assigned to the coupling between the L-a and L-b pi pi* surfaces, and to the system evolution along the dissociative pi sigma* state. (C) 2012 Elsevier B. V. All rights reserved.