A new one-step synthetic protocol of tris-functionalized Anderson polyoxomolybdates directly from heptamolybdate salts was presented in this Communication. Through this new method, we obtained the first example of Anderson-type polyoxomolybdates with vanadium as the heteroatom. Moreover, the crystals of the products exhibited interesting nanocage or framework extended structures, which were greatly affected by the trialkoxyl ligands as well as the counterions.