The title species are synthesized in the gas phase and their unimolecular chemistry is determined by a combination of tandem mass spectrometry methods. Dissociative electron ionization of the α-amino acids valine, leucine, isoleucine, or serine produces the α-glycyl cation, H2NCH+COOH, in high yield and purity. At threshold, this ion dissociates by CO loss to form the proton-bound complex HC≡N…H+…OH2 via a tight 1,4-H migration that is associated with a high reverse barrier. After collisional activation, additional channels open, most notably the formation of the complementary and structure-characteristic fragments H2NCH+· (ionized aminocarbene) and +COOH and the elimination of OH·. Charge reversal and neutralization—reionization of H2NCH+COOH conclusively show that α-glycyl anion, H2NCH−COOH, and α-glycyl radical, H2NCH·COOH, are stable species residing in deep potential energy wells. In the microsecond time window of the experiments, a small fraction of the α-glycyl radical decomposes by sequential elimination of H2O and CO. The α-glycyl anions arising by charge reversal of the cation or reionization of the radical partly undergo rearrangement losses of H2 and H2O, direct cleavages to −COOH, OH−, and H2N−, and consecutive fragmentation of these primary product anions.