Sm3+/Eu3+ co-doped calcium borophosphate phosphors were synthesized by solid state reaction method. 2CaO-B2O3-P2O5: Sm3+/Eu3+ co-doped phosphors were characterized by XRD, SEM, DRS, FT-IR, 31P solid state NMR, excitation, photoluminescence (PL) and decay profiles. XRD profiles showed that the prepared phosphors exhibit a hexagonal phase in crystal structure and SEM results showed that the particles are more irregular morphologies. FT-IR spectrum shows prominent band at 1029 cm-1 which is due to the asymmetric stretching vibrations of [PO4]3- tetrahedrons. From 31P NMR spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 (CBP) phosphors, it was observed that the chemical shifts are located in the positive frequency region indicating the presence of mono-phosphate complexes Q0-(PO43-). Photoluminescence spectra of Sm3+/Eu3+ co-doped CBP phosphors show increase in emission intensity of Eu3+ ion due to co-doping with Sm3+ ions due to energy transfer process. The energy transfer mechanism between Sm3+ and Eu3+ ions has been clearly explained. The energy transfer process has been evidenced by lifetime decay profiles. From CIE chromaticity diagram, pure red color emission was observed in 0.6Sm3+/0.6Eu3+ co-doped CBP phosphors. These results suggest that the prepared phosphors are potential for red luminescent optical materials.