By the oxidation of decavanadate {n-Bu4N}(4)[V10O26] in the presence of F- and Pd(NO3)(2) in dimethyl sulfoxide (DMSO), a palladium-supported fluoride-incorporated dodecavanadate, {n-Bu4N}(4)[{Pd(NO3)(DMSO)}(2)V12O32(F)(2)]center dot 2DMSO (1), was synthesized. The dodecavanadate component consisted of ten VO5 units and two VO4 units in the framework with two fluorides inside the framework and each VO4 unit was coordinated to Pd2+. The (VNMR)-V-51 spectrum showed four peaks at -444, -458, -525, and -542 ppm with the intensity ratio of 2:1:2:1, showing the stability of 1 in the solution state.