LiCa3MgV3O12:Bi3+ phosphor is successfully synthesized by the high-temperature solid-state reaction method in air. The crystal structures and luminescence properties are investigated. Excitation/emission bands of LiCa3MgV3O12:Bi3+ phosphor show red-shift with increasing the monitored/excitation wavelengths from short to long. The doping of Bi3+ ion can result in the host LiCa3MgV3O12 lattice distortion and the energy transfer (ET) from VO43- to Bi3+. The tunable emission of phosphor from blue-green to yellow can be observed with increasing Bi3+ concentration from 0 to 8 mol%. The chromaticity coordinates of LiCa(3-x)MgV3O12:xBi(3+) phosphors can change from (0.2393, 0.3260) to (0.4358, 0.4472) with increasing Bi3+ concentration from 0 to 8 mol%. The existence of VO43- -> Bi3+ ET in LiCa3MgV3O12:Bi3+ phosphor is indicated by the luminescence properties. The luminous mechanism of LiCa3MgV3O12:Bi3+ phosphor is explained by the configurational coordinate diagrams of VO43- and Bi3+. The experimental results are helpful for the luminescence property researches of other Bi3+ -doped luminescence materials.