With the successful synthesis of NaLn(WO 4 ) 2 for the full spectrum of Ln, the effects of lanthanide contraction on the structural features, crystal morphology, and IR responses of the compounds were clarified. The temperature-and timecourse phase/morphology evolutions and the phase conversion upon calcination were thoroughly studied for the Group I and Group II compounds with Ln=La and Lu for example, respectively. Unknown intermediates were characterized by elemental analysis, IR absorption, thermogravimetry, and differential scanning calorimetry to better understand their chemical composition and coordination. The photoluminescence properties of NaEu(WO 4 ) 2 and NaTb(WO 4 ) 2 , including excitation, emission, fluorescence decay, and quantum efficiency of luminescence, were also comparatively studied for the as-synthesized and calcination products.