Sm³⁺-activated Ca₂SiO₄ red phosphors were prepared by the conventional high-temperature solid-state reaction method, and the effects of sodium (Na⁺) and samarium (Sm³⁺) ions doping concentrations on their crystal structure and luminescent properties were investigated by X-ray diffraction (XRD) and fluorescent spectrofluorometer. XRD patterns demonstrate that a well-crystalline structure forms in the phosphors when they are treated by calcination at 1200℃ for 4 h, and the excitation spectra exhibit good absorption in the range between 350 and 420 nm. Under the irradiation of 405 nm near-ultraviolet (NUV) light, the spectra of the phosphors show a main emission peak at 601 nm attributed to the ⁴G_5/2→⁶H_7/2 transition of Sm³⁺ ions, and its intensity is greatly influenced by the concentrations of Sm³⁺ and Na₂CO₃. When the concentrations of Sm³⁺ ions and Na₂CO₃ are 2mol% and 6mol%, respectively, the optimal emission intensity can be obtained. From strong absorption in the near ultraviolet zone, the Na_0.06Sm_0.02Ca_1.92SiO₄ phosphor is a promising red-emitting phosphor for white light emitting diodes (W-LEDs).