A question of how electrons can escape from one-atom-thick surfaces has seldom been studied and is still not properly answered. Herein, lateral electron emission from a one-atom-thick surface is thoroughly studied for the first time. We study electron emission from side surface of individual electrically biased carbon nanotubes (CNTs) both experimentally and theoretically and discover a new electron emission mechanism named phonon-assisted electron emission. A kinetic model based on coupled Boltzmann equations of electrons and optical phonons is proposed and well describes experimentally measured lateral electron emission from CNTs. It is shown that the electrons moving along a biased CNT can overflow from the one-atom-thick surface due to the absorption of hot forward-scattering optical phonons. A low working voltage, high emission density, and side emission character make phonon-assisted electron emission primarily promising in electron source applications.