RbCaGd(PO4)2 doped with Ce3+, Mn2+ was synthesized by the sol-gel method. The crystal structure and crystallographic location of Ce3+ in RbCaGd(PO4)2 were identified by Rietveld refinement. Powder X-ray diffraction (XRD) revealed that the structure of RbCaGd(PO4)2:Ce3+ compounds is hexagonal structure which is similar to that of hexagonal LnPO4 with the lattice constant of a=b=7.005(57)Å, c=6.352(05)Å, and V (cell volume)=269.980Å3. The photoluminescence behavior and emission mechanism were studied systematically by doping activators in the RbCaGd(PO4)2 host. The Mn2+ incorporated RbCaGd(PO4)2:Ce3+, Mn2+ compounds exhibited blue emission from the parity- and spin-allowed f-d transition of Ce3+ and orange-to-red emission from the forbidden 4T1→6A1 transition of Mn2+. The emission chromaticity coordinates of RbCaGd(PO4)2:0.10Ce3+, xMn2+ (x=0.16, 0.25) are close to the white region due to an energy transfer process and the energy transfer mechanism from Ce3+ to Mn2+ in the RbCaGd(PO4)2 host was dominated by dipole-dipole interactions.