A Ce3+-based layered perovskite compound, Dion-Jacobson type RbCeTa2O7, has been discovered for the first time by introducing only a trivalent cerium ion to form [CeTa2O7]- layers. The unique green color was experimentally and theoretically ascribed to two charge transfer transitions of ligand-to-metal O2p → Ce4f and metal-to-metal Ce4f → Ta5d.