In this paper, CaMoO₄∶xDy³⁺(x=0.01~0.05) and CaMoO₄∶0.03Dy³⁺/ySm³⁺(y=0.01~0.05) series phosphors and CaMoO₄ matrix were synthesized by hydrothermal method using hexadecyl trimethyl ammonium bromide as complexing agent. The effects of Dy³⁺ doping and Dy³⁺/Sm³⁺ co-doping on the structure, morphology and luminescent properties of the samples were investigated. The results show that Dy³⁺ doping and Dy³⁺/Sm³⁺ co-doping do not change the tetragonal phase of CaMoO₄, but the lattice parameters decrease. The micromorphologies of all samples are ellipsoidal. Under the excitation of 353 nm, the strongest emission peak of CaMoO₄∶xDy³⁺ phosphor is located at 575 nm, which is due to the ⁴F_9/2→⁶H_13/2 dipole transition of Dy³⁺, and the optimal doping molar concentration is x=0.03. Under the excitation of 298 nm, the quenching molar concentration of Sm³⁺ in CaMoO₄∶0.03Dy³⁺/ySm³⁺ phosphor is y= 0.03. The intrinsic emission of rare earth Dy³⁺ and Sm³⁺ are obtained through CaMoO₄ matrix energy transfer, and the energy transfer of Dy³⁺ to Sm³⁺ is also observed. Under the excitation of 405 nm, the CIE coordinates of CaMoO₄∶0.03Dy³⁺/ySm³⁺(y=0.01~0.05) change from cyan region to white region, and the CaMoO₄∶0.03Dy³⁺/ySm³⁺(y=0.03~0.05) phosphors exhibit white emission. Therefore, Dy³⁺/Sm³⁺ co-doped CaMoO₄ phosphor is a single matrix white LED phosphor with potential application value.