La2MoO6 orange-red phosphors with high efficiency incorporated with Eu, Dy and Sm have been synthesized through a gel combustion method. The influences of rare earth doping in synthesized samples were analysed by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and cathodoluminescence. Rare earth doped La2MoO6 samples show strong emission bands in the range of 400–750 nm and optimal doping concentration for all samples was 2 mol%. La2MoO6 host doped Eu ion showed intense and predominant emission peaks in 450–750 nm range. The electrical multipolar interaction contributed to the non-radiative energy transfer between Eu3+ ions in La2MoO6 host matrix. Sm doped La2MoO6 host exhibited orange-red CL emission peaks at 564, 608, 652 and 708 nm La2MoO6:Dy3+ phosphor displayed emissions at 484, 574 and 670 nm, respectively. The observed intense and sharp emission peaks indicate that La2MoO6 is promising host for lanthanides doped phosphor materials in the applications of optoelectronic.