Mapping by angle-resolved photoemission spectroscopy of the spectral functions of graphite and graphene layers at low temperatures reveals a heretofore unreported gap of ~ 67 meV at normal emission. This gap persists to room temperature and beyond, and diminishes for increasing emission angles. We show that this gap arises from electronic coupling to out-of-plane vibrational modes at the K(¯) point in the surface Brillouin zone in accordance with conservation laws and selection rules governed by quantum mechanics. Our study suggests a new approach for characterizing phonons and electron-phonon coupling in solids.