The complete valence shell binding energy spectra and valence orbital electron momentum distributions for NH 3 have been measured by high-momentum-resolution electron momentum spectroscopy (EMS). The results are quantitatively compared with theoretical calculations using SCF wavefunctions ranging from DZ quality to a newly developed 126-GTO wavefunction essentially at the Hartree-Fock limit. The 3a 1 and to a lesser extent the 2a 1 valence orbital are not adequately described even at the Hartree-Fock limit with basis set saturation including diffuse functions. The differences between theory and experiment are largely resolved by ion-neutral overlap calculations using CI wavefunctions to incorporate the effects of electron correlation. The 126-G (CI) wavefunctions provide accurate calculation of a wide range of electronic properties of NH 3 and also give good quantitative prediction of the three valence orbital momentum distributions as well as a reasonable prediction of the many-body pole strength distribution observed in the (2a 1) −1 inner valence binding energy spectrum. The present EMS results are compared with recent investigations of wavefunction tails by exterior electron distribution calculations and Penning ionization electron spectroscopy measurements reported by Ohno et al.