A series of NaLaTi2O6: Eu3+ red phosphors with different Eu3+ ion concentrations were prepared via a high-temperature solid-state reaction technique. The effects of Eu3+ ion concentration and temperature on the fluorescent properties of NaLaTi2O6: Eu3+ phosphors were investigated. The XRD patterns revealed that the as-synthesized samples were single-phase NaLaTi2O6. Eu3+ ion concentration-dependent excitation and emission spectra showed that there was an efficient energy transfer from NaLaTi2O6 host to Eu3+ ions. Concentration quenching was observed and can be ascribed to exchange interaction between Eu3+ ions based on Van Uitert's model. According to the temperature-dependent emission spectra and the fluorescence decay curves, crossover process was confirmed to be the main mechanism for the temperature-dependent fluorescence quenching behavior of D-5(0) level of Eu3+ ions in NaLaTi2O6 phosphors. The activation energy was obtained to be 0.30 eV by Arrhenius model. Based on the emission spectra and Judd-Ofelt theory, the optical transition properties of Eu3+ ions in NaLaTi2O6 phosphors were studied.