Penning ionization of 2-aminoethanol (AE), ethylamine (EA), N-methyl-2-aminoethanol (MAE), and 2-methoxy-N-methylethylamine (MMA) upon collision with He*(2(3)S) metastable atoms has been studied by two-dimensional electron-energy/collision-energy-resolved Penning ionization electron spectroscopy (2D-PIES) in connection with intramolecular hydrogen bonding of (OHN)-N-... and (NHO)-O-... types. In AE and MAE, (OHN)-N-... type hydrogen bonds were found to be preferentially formed, whereas in MAE, observed data gave a confirmation of the (NHO)-O-... type hydrogen bond. Effects of hydrogen bond formation were observed for ionization bands of nonbonding orbitals related to the hydrogen bond. Associated with hydrogen bond formation, the relative and the peak energy shift becomes much less negative.