The tetragonally double alkaline rare earth molybdates NaRe(MoO 4 ) 2 (Re = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Er) micro-particles in aqueous solution of Re(NO 3 ) 3 and Na 2 MoO 4 were prepared hydrothermally by a facile and effective EDTA-assisted method, and investigated by XRD, SEM, FE-SEM, photoluminescence (PL) excitation and emission spectra. The results showed that the radii of Re ions, pH and the molar ratio of Re(NO 3 ) 3 /Na 2 MoO 4 in the synthesis solution play an important role in controlling sizes, morphologies and luminescent properties of the final products. And the possible formation mechanism for the bipyramid-like structure and role of EDTA were discussed in detail. The microstructure and PL property of NaY x La 1-x (MoO 4 ) 2 :10%Eu 3+ was investigated, and it showed that NaY 0.5 La 0.5 (MoO 4 ) 2 exhibited regular sphere-like morphology and emitted the stronger red emission with better color purity than other products.