Sm3+-doped Li2BaSiO4∶Sm3+ phosphor is prepared by a solid-state reaction method. Through X-ray diffraction (XRD) data, Li2BaSiO4∶Sm3+ with hexagonal crystal structure is synthesized at 850 ℃, and the diffraction peak of XRD move to the high- angle and the lattice distortion increase as increasing the mass fraction of Sm3+ ions. The Li2BaSiO4∶Sm3+ material has strong absorption at 330~500 nm and can be excited effectively by near ultraviolet and blue light emitting diode (LED) chip. The maximum emission intensity of Sm3+ and the minimum ratio of I650/I607 are attained by doping 1.5% Sm3+ . The results suggest that Sm3+ ions prior to occupy Ba2+ with symmetric lattice in the Li2BaSiO4 materials. The emission peaks located at 518, 563, 607, 650 and 707 nm are presented under the excitation of 402 nm. The spectrum of 518 nm is attributed to defect luminescence in Li2BaSiO4∶Sm3+ , while others are derived from the emission of 4G5/2→6HJ (J=5/2，7/2，9/2，11/2) of Sm3+ . The color coordinate of Li2BaSiO4∶Sm3+ sites in yellow range due to defect emission, and the formation mechanism for defect luminescence is discussed.