[en] Highlights: • The NaH₂O complex describes the first step of the solvation of Na. • Photoelectron imaging reveals how solvation modifies the electronic structure of Na. • A remarkably complex structure of electronic levels with multiple crossings is found. • The first excited p-states fall into two classes. 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 “p_π-states” with flat potential curves in the intermolecular degrees of freedom, and the latter to the excitation via the “p_σ-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.