Measured single-photon zero-kinetic-energy pulsed field ionization (ZEKE-PFI) photoelectron spectra of the sodium-water complex are presented and compared with the results of rotationally resolved ab initio calculations. The very nonatomiclike behavior of the photoionization of this Na(H2O) complex is essential in accounting for several significant features in these spectra. Agreement between the calculated and measured photoelectron spectra is encouraging. Furthermore, these results suggest that combined experimental and theoretical studies of ZEKE-PFI spectra can be very useful in elucidating the molecular structure and intermolecular force fields of small clusters.