Angle-resolved photoemission spectroscopy (ARPES) study of a layered electride Ca2N was carried out to reveal its quasi-two-dimensional electronic structure. The band dispersions and the Fermi-surface map are consistent with the density functional theory results except for a chemical potential shift that may originate from the high reactivity of surface excess electrons. Thus, the existence of anionic excess electrons in the interlayer region of Ca2N is strongly supported by ARPES.