Self-activated phosphors have attracted considerable attention due to their low synthesis temperature, high excitation threshold, and broad emission spectrum. And self-activated tungstate phosphors are distinguished by their low cost and stable chemical properties. Generally, it is difficult to observe luminescence from tungstate phosphors at room temperature. Furthermore, blue-emitting tungstate phosphors with high quantum efficiency are rarely reported. In this study, we succeeded in discovering high quantum-efficiency bluish-white-emitting Li 2 (Mg x Zn 1- x ) 2 W 2 O 9 phosphors and investigating their detailed crystal structures. Upon near-ultraviolet excitation at 266 nm, these phosphors exhibit a broadband emission peak. The red shift of emission is slight with increasing Zn content in Li 2 (Mg x Zn 1- x ) 2 W 2 O 9 . A highly compact octahedral [WO 6 ] unit is observed in the Li 2 (Mg x Zn 1- x ) 2 W 2 O 9 phosphors. The phosphors exhibit high internal quantum efficiencies (IQEs) of 68.70% (M = Mg), 43.90% (M = Mg 0.5 Zn 0.5 ), and 22.90% (M = Zn), respectively. This study provides a bluish-white-emitting tungstate phosphor with high quantum efficiency.