The gas phase structure and excited state dynamics of o-aminophenol-H2O complex have been investigated using REMPI, IR-UV hole-burning spectroscopy, and pump-probe experiments with picoseconds laser pulses. The IR-UV spectroscopy indicates that the isomer responsible for the excitation spectrum corresponds to an orientation of the OH band away from the NH2 group. The water molecule acts as H-bond acceptor of the OH group of the chromophore. The complexation of o-aminophenol with one water molecule induced all enhancement in the excited state lifetime on the band origin. The variation of the excited state lifetime of the complex with the excess energy from 1.4 +/- 0.1 ns for the 0-0 band to 0.24 +/- 0.3 ns for the band at 0-0 + 120 cm(-1) is very similar to the variation observed in the phenol-NH3 system. This experimental result suggests that the excited state hydrogen transfer reaction is the dominant channel for the non radiative pathway. Indeed, excited state ab initio calculations demonstrate that H transfer leading to the formation of the H3O center dot radical within the complex is the main reactive pathway.