Red-emitting CaGd2-x-y(WO4)(4):xEu(3+),ySm(3+) phosphors have been synthesized by the solid state reaction method. The crystal structure and luminescent properties have been investigated by X-ray powder diffraction (XRPD) and photoluminescence spectra. The results show that CaGd2(WO4)(4) phosphor has monoclinic system with space group I2/b. CaGd2(WO4)(4):Eu3+,Sm3+ phosphor can be effectively excited by near-UV, and the emission spectrum exhibits the strongest red emission peak corresponding to the D-5(0) -> F-7(2) transition of Eu3+ ions. The effective energy transfer from Sm3+ to Eu3+ in CaGd2(WO4)(4):Eu3+,Sm3+ has been confirmed by photoluminescence and decay measurement, and the energy transfer efficiency is calculated to be 23.34%. Furthermore, the temperature dependent luminescence of the CaGd2(WO4)(4):Eu3+,Sm3+ phosphor has been studied, and the thermal activation energy Delta E is found to be 0.305 eV. These results show that CaGd2(WO4)(4):Eu3+,Sm3+ phosphor can be a potentially better red emitting phosphor for white light emitting diodes (LEDs). (C) 2017 Published by Elsevier Ltd.