A novel class of orange-red phosphors based on Eu3+-activated LaNbTiO6 was successfully fabricated by a wet chemical method, called a modified combustion approach. XRD, TG-DTA, SEM, and EDS results show that the heat-treatment of the powders above 1000 degrees C is enough to obtain highly crystallized and phase-pure LaNbTiO6 and Eu3+-doped samples, which is of prime importance in investigating the optical properties of the novel phosphors using LaNbTiO6 as the host material. UV-vis diffuse reflectance spectroscopy reveals that the direct band gap of LaNbTiO6 with large grains (above 200 nm) is calculated to be 3.27 eV, while the absorption edge of the small particles shows an obvious blue-shift. Two blue emission bands centered at 440 and 470 nm ascribed to the self-trapped exciton emission of the distorted NbO6 and TiO6 groups for the pure LaNbTiO6 can be obtained. Photoluminescence spectra of the Eu3+-doped phosphor particles illuminated the simultaneous occurrence of several intense orange-red band emissions due to the characteristic transitions of D-5(0,1) -> F-7(J) (J = 0, 1, 2, 3, 4) of EU3+ under 395 nm excitation. The mechanism of these multiplets possibly arising from the odd-parity distortions of the Eu3+ ion environment and the effect of crystallanity of the compounds on luminescence were discussed, respectively. The highly bright and color-uniform fluorescence images of the doped samples with short luminescence decay times (nanosecond magnitude) confirmed the potential applications of the phosphors in luminescence and display devices.