Trivalent samarium doped barium molybdate(BaMoO_4:Sm~(3+)) red phosphor was successfully synthesized by hydrothermal method. The crystal structure, morphology and photoluminescent property were characterized by X-ray diffraction, field environmental scanning electron microscopy and photoluminescence spectroscopy. The results indicated that the synthesized BaMoO_4:Sm~(3+)phosphor consisted of a pure phase with an octahedral structure. The main excitation peaks were located at 362, 404, 445 and 477 nm, respectively, and were obviously observed. The main emission peaks were located at 533, 566, 602 and 646 nm, respectively. The phosphors exhibited a red performance at 646 nm, which was appropriate for the ultraviolet-light emitting diode(UV-LED) and blue LED. The luminescent intensity of BaMoO_4:Sm~(3+) increased with an increase in the doping amount of Sm~(3+). The luminescent intensity had the optimal value for x=0.03. When the doping amount of Sm~(3+) was further increased, the concentration quenching phenomenon was observed. Monovalent lithium(Li+) cation was used as a charge compensator. The luminescence intensity first increased with increasing Li+ doping concentration, and then decreased. The optimal content of Li+ was about 2%. The BaMoO_4:Sm~(3+) phosphor prepared in this study could act as superior red phosphor for white LEDs. Trivalent samarium doped barium molybdate (BaMoO_4: Sm ~ (3+)) red phosphor was successfully synthesized by hydrothermal method. The crystal structure, morphology and photoluminescent property were characterized by X-ray diffraction, field environmental scanning electron microscopy and photoluminescence spectroscopy. results indicate that the synthesized BaMoO_4: Sm ~ (3+) phosphor consisted of a pure phase with an octahedral structure. The main excitation peaks were located at 362, 404, 445 and 477 nm, respectively, and were apparent observed. The phosphors exhibited a red performance at 646 nm, which was appropriate for the ultraviolet-light emitting diode (UV-LED) and blue LED. The luminescent intensity of BaMoO_4: Sm (3+) increased with the increase in the doping amount of Sm ~ (3+). The luminescent intensity had the optimal value for x = 0.03. When the doping amount of Sm ~ (3+) was further increased, the concent The luminescence intensity first increased with increasing Li + doping concentration, and then decreased. The optimal content of Li + was about 2%. The BaMoO_4: Sm ~ ( 3+) phosphor prepared in this study could act as superior red phosphor for white LEDs.