Rare-earth ions co-activated red phosphors Ca3(VO4)2: Eu3+, Sm3+ were synthesized by modified solid-state reactions. The samples were characterized by X-ray powder diffractometer (XRD), energy-dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and luminescence spectrometer (LS). The results showed that the Eu–Sm system exhibits higher emission intensity than those of the Eu single-doped system and Sm separate-doped system under blue light. Samarium (III) ions are effective in broadening and strengthening absorptions around 467 nm. Furthermore, they exhibit enhanced luminescence emission. Luminescent measurements showed that the phosphors can be efficiently excited by ultraviolet (UV) to visible region, emitting a red light with a peak wavelength of 616 nm. The material has potential application as a phosphor for light-emitting diodes (LEDs).