Extensive attention has been focused toward studies on inexpensive and rare-earth-free garnet-structure vanadate phosphors, which do not have a low optical absorption due to the luminescence color being easily controlled by its high composition flexibility. However, bluish emission phosphors with a high quantum efficiency have not been found until now. In this study, we successfully discovered bluish-white emitting, garnet structure-based LiCa3MV3O12 (M = Zn and Mg) phosphors with a high quantum efficiency, and the detailed crystal structure was refined by the Rietveld analysis technique. These phosphors exhibit a broad-band emission spectra peak at 481 nm under near UV-light excitation at 341 nm, indicating no clear difference in the emission and excitation spectra. A very compact tetrahedral [VO4] unit is observed in the LiCa3MV3O12 (M = Zn and Mg) phosphors, which is not seen in other conventional garnet compounds, and generates a bluish-white emission. In addition, these phosphors exhibit high quantum efficiencies of 40.1% (M = Zn) and 44.0% (M = Mg), respectively. Therefore, these vanadate garnet phosphors can provide a new blue color source for LED devices.