The white LEDs phosphor used currently mainly are blue GaN chip which excites yellow, green, and red earth phosphor. The technology of yellow and green phosphor has been mature, while red phosphor with stable performance is relatively rare. Therefore, a new type of red phosphor excited by blue light needs to be developed. In this paper, compared with the traditional high temperature solid-phase synthesis method, a series of efficient spherical monodisperse calcium tungstate red luminescent materials CaWO4∶Sm3+ and CaWO4∶Eu3+ with high luminescent performance were synthesized with hydrothermal method at lower temperatures 160 ℃. The crystal structure, surface topography and optical characteristics of the prepared samples were measured with X-ray powder diffraction (XRD), field emission scanning electron microscope (FE-SEM), and fluorescence spectroscopy (PL). The effect of the doping concentration, reaction time and other conditions on the morphology and fluorescence properties of the samples had been studied. The results show that doping concentration affects not only the morphology of the prodcucts, but also the fluorescence intensity of light-emitting phosphor.CaWO4:Sm3+ and CaWO4∶Eu3+ present the most efficient light-emitting performance when the doping concentration of the Sm3+ and Eu3+ are 6% and 4%, respectively. According to the results above, CaWO4∶Sm3+ and CaWO4∶Eu3+ can be used as a phosphor materials of fluorescent lamp and blue chip LED.