Eu³⁺，Sm³⁺ doped Y₂MoO₆ red and orange phosphors have been prepared by a sol-gel method. The crystals structure, morphologies and optical properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence emission spectra (PL), excitation spectra (PLE) and decay curves (lifetime) respectively. XRD results imply that the obtained samples are of monoclinic structure with C2/c space group and no extra phases are observed. The sample size of sub-micrometer is shown in SEM images. The samples can absorb near UV light efficiently confirmed by PLE spectra and reveal excellent red and orange emissions. Furthermore, the luminescence mechanism, the effect of concentration quenching and the CIE chromaticity coordinates are discussed in detail. These phosphors will have potential applications in phosphor-converted WLEDs for the excitation of near UV light.