The tetragonally double alkaline rare earth molybdates NaRe(MoO4)2 (Re = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Er) micro‐particles in aqueous solution of Re(NO3)3 and Na2MoO4 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(NO3)3/Na2MoO4 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 NaYxLa1‐x(MoO4)2:10%Eu3+ was investigated, and it showed that NaY0.5La0.5(MoO4)2 exhibited regular sphere‐like morphology and emitted the stronger red emission with better color purity than other products. When Tm3+, Dy3+ and Eu3+ with appropriate concentrations were used as dopants to modify this bipyramid NaY(MoO4)2 material, the white light emission material of NaY(MoO4)2:1%Tm3+‐11%Dy3+‐0.6%Eu3+ was successfully synthesized and its CIE chromaticity coordinates is (0.33, 0.33), which is the standard white light point. These novel white‐light‐emitting NaY(MoO4)2:1%Tm3+‐11%Dy3+‐0.6%Eu3+ with single phase would be a promising material in the WLED field.