As host materials, phosphate compounds offer great potential for lanthanides to display luminescence characteristics. In this work luminescence behaviour of Na2CaP < sub>2O7:RE 3+ are presented for the first time. Na2CaP < sub>2O7 novel phosphors activated with the trivalent rare earth ions ((RE = Ce, Eu, Tb, Sm) were synthesized by solid state diffusion method. Phosphors were characterized for phase purity and luminescent properties. The emission and excitation spectra were followed to explore the luminescence attributes. The as prepared powders of Ce 3+ , Eu 3+ ,Tb 3+ and Sm 3+ doped Na2CaP < sub>2O7 emit near-uv, red, green and orange reddish light as result of f-d and f-f transitions respectively. The study is novel as no such luminescence data are available for this compound. The results are promising in view of the requirement for pc-white LEDs for solid state lighting applications.