CaWO4:Smx(x=0, 0.5, 1.0, 1.5, 2.0mol%) white phosphors with different concentrations of Sm3+ ions weresynthesized using the hydrothermal method. The crystal structure, surface, and optical properties of the CaWO4:Smphosphors were investigated using X-ray diffraction(XRD), field-emission scanning electron microscopy(FE-SEM),photoluminescence(PL) and photoluminescence excitation(PLE). From the XRD results, the crystal structure of theCaWO4:Sm phosphors was found to be tetragonal. The CaWO4:Sm phosphors became more cohesive with increasing Sm3+-ion concentration. The photoluminescence excitation(PLE) peak of the phosphors, at around 250nm, was ascribed to thetransition from the 1A1 ground-state to the high-vibration level of 1T2 in the WO42− complex. The maximum emissionspectra of the phosphors were observed when the Sm3+ concentration was 0.5mol%. The luminescence intensity of theCaWO4 phosphors was decreased for Sm3+ concentrations greater than 0.5mol%.