The gas-phase chemistry of deprotonated benzyl N-phenylcarbamates was investigated by electrospray ionization tandem mass spectrometry. Characteristic losses of a substituted phenylcarbinol and a benzaldehyde from the precursor ion were proposed to be derived from an ion-neutral complex (INC)-mediated competitive proton and hydride transfer reactions. The intermediacy of the INC consisting of a substituted benzyloxy anion and a phenyl isocyanate was supported by both ortho-site-blocking experiments and density functional theory calculations. Within the INC, the benzyloxy anion played the role of either a proton abstractor or a hydride donor toward its neutral counterpart. Relative abundances of the product ions were influenced by the nature of the substituents. Electron-withdrawing groups at the N-phenyl ring favored the hydrogen transfer process (including proton and hydride transfer), whereas electron-donating groups favored direct decomposition to generate the benzyloxy anion (or substituted benzyloxy anion). By contrast, electron-withdrawing and electron-donating substitutions at the O-benzyl ring exhibited opposite effects.