To develop the bright-vivid red- and yellow-inorganic fluorescent pigments with high luminescence properties,A3V5O14 (A = K and Rb) and Cs2V4O11 inorganic pigments were synthesized by a water assisted solid state reaction (WASSR)method and a conventional solid state reaction method. Although impurity peaks corresponding to the AVO3 and AV3O8(A = K, Rb, and Cs) were observed in all samples prepared, the trigonal structure A3V5O14 (A = K and Rb) and orthorhombicstructure Cs2V4O11 were successfully obtained as a main phase. These inorganic pigments showed the broad absorption band(under 550 nm) originated from CT transitions of VO4 polyhedron, and the strong broad red- and green-emission bands dueto 3T2 1A1 and3T1 1A1 transitions of the [VO4]3 group. The A3V5O14 (A = K and Rb) and Cs2V4O11 pigments showeda bright-vivid red- and yellow-body color, where the a* values of the A3V5O14 (A = K and Rb) were +35.5 and +45.9,respectively, and b* value of Cs2V4O11 pigments was +50.3. The L* values of the A3V5O14 (A = K and Rb) and Cs2V4O11inorganic pigments were over +45. These results indicate that the A3V5O14 (A = K and Rb) and Cs2V4O11 inorganic pigmentscould be an attractive candidate as a bright-vivid red- and yellow inorganic pigments.