The energetics and lifetimes of the first electronically excited states ("3p-states") of NaH2O and NaD2O have been measured by pump-probe (740/780 and 400 nm) photoelectron imaging. The photoelectron spectra of NaH2O show two bands at an electron kinetic energy of 0.14 and 0.38 eV, respectively. We assign the former to excitation via the two energetically close lying "pp-states" with flat potential curves in the intermolecular degrees of freedom, and the latter to the excitation via the "pr-state" characterized by significantly steeper potential curves. The relaxation of all "p-states" follows a double exponential decay with a lifetime around 110 ps for the dominant fast component. (C) 2017 Elsevier B.V. All rights reserved.