Eu3+ doped NaLa(MoO4)2 microcrystals with different sizes are synthesized by a mild hydrothermal method, and the morphologies of the microcrystals can be easily controlled by adjusting the volume ratio of ethylene glycol to water and the aging time. Uniform high-quality shuttle-like microcrystals with an average length of 2.0 m are obtained under the hydrothermal condition of 180℃ for 16 h. From the emission spectra of NaLa(MoO4)2∶Eu3+ microcrystals, it is concluded that the dopant Eu3+ ion occupies a La3+ site. It is indicated that the concentration quenching of the emission peak at 613 nm of Eu3+ is ascribed to the electric dipole-electric quadrupole interaction, and the cross relaxation process of Eu3+(5D1 ) + Eu3+(7F0 ) Eu3+( 5D0 ) + Eu3+(7F3) appear.