The binding energy spectra and electron momentum distributions for the outer-valence molecular orbitals of gaseous cyclopropylamine (CPA) have been measured by (e, 2e) electron momentum spectrometer employing noncoplanar asymmetric geometry at the impact energy of 2500 eV. The experimental results are interpreted on the basis of the quantitative calculations of the ionization energies and the relevant molecular orbitals at benchmark theoretical levels using the outer-valence Green's function method, the symmetry-adapted cluster configuration interaction method, and the density functional theory with B3LYP hybrid functional. The total energies of the trans and gauche conformers of CPA are also calculated by the second-order Moller-Plesset perturbation theory with large basis sets and the derived enthalpy differences (2.02-2.12 kcal/mol) are consistent with the previous experimental data (2.19 kcal/mol). The theoretical binding energy spectra and electron momentum distributions, in which the relative abundances of trans and gauche are taken into account, are generally in accordance with the experimental results except for the ionization band from the trans 8a' and gauche 11 a orbitals. The discrepancy is explained qualitatively in view of the picture of molecular geometry change at the instant of ionization.