Uniform orange-to-red spherical phosphors of Sr2P2O7:Ce3+, Mn2+ have been synthesized by the co-precipitation method and characterized by X-ray powder diffraction, scanning electron microscopy, and photoluminescence spectroscopy. The results indicate that the morphology, size, and photoluminescence properties of Sr2P2O7:Ce3+, Mn2+ phosphors can be effectively controlled by the reaction and the sintering temperatures. Energy transfer from Ce3+ to Mn2+ in Sr2P2O7 phosphor was observed from photoluminescence spectra of Sr2P2O7:Ce3+, Sr2P2O7:Mn2+, and Sr2P2O7:Ce3+, Mn2+. Moreover, based on a self-assembly process, a possible formation mechanism for the spherical phosphors is proposed. The uniform phosphor spheres obtained in this work exhibit great potential for high-resolution display devices such as light emitting diodes.