A series of red-orange luminescent Y2-2xMgTiO6∶2xSm3+(YMT∶2xSm3+, 0≤x≤0.11) phosphors were synthesized by sol-gel method. The samples were characterized and analyzed by powder X-ray diffractometer (XRD), scanning electron microscopy (SEM), photoluminescence excitation and emission spectroscopy. The results show that the as-prepared YMT∶Sm3+ exhibits a pure-phase structure with no impurity phases. The SEM images show an average diameter of about 2~3μm for the particles and good dispersibility without overt agglomeration phenomenon. Under the excitation of a 407nm near-ultraviolet light, the emission spectrum of YMT∶Sm3+ phosphors has three significant emission peaks in the wavelength range of 500~700nm, which are the stronger orange-red light emission at 603nm (4G5/2→6H7/2) and 650nm (4G5/2→6H9/2), and the weaker green light emission at 569nm (4G5/2→6H5/2). The optimal doping concentration of Sm3+ ions is about 5mol%, and the theoretically calculated critical transfer distance of Sm3+ ions is 1.619nm. When the concentration of Sm3+ exceeds 5mol%, there is an obvious concentration quenching effect, which is attributed to the electric quadrupole-electric quadrupole (q-q) interaction between Sm3+ ions. The CIE chromaticity coordinates of YMT∶Sm3+ phosphors are located in the orange-red region, indicating that it has potential application value in red phosphors for white LEDs.