The striking aesthetic appeal of fullerene‐like clusters has captured the interest of researchers. Nevertheless, the assembly of fullerene‐like polyoxovadanadate (POV) cages remains a significant challenge due to the scarcity of suitable pentagonal motif. Herein, we have successfully synthesized the first fullerene‐like all‐inorganic POV cage, {(V2O)V30Nb12O102(H2O)12} (V30Nb12), by introducing Nb into the POVs. V30Nb12 is assembled by 12 heterometallic {(Nb)V5} pentagons through sharing V centers with Ih symmetry, reminiscent of C60. To our knowledge, the fullerene‐like V30Nb12 not only represents the highest‐nuclearity POV cage but also stands as the first niobovanadate cluster. Notably, V30Nb12 exhibits excellent solution stability, as confirmed by ESI‐MS, FT‐IR and UV‐vis spectra. As there is no protection organic ligand on its outer surface, V30Nb12 can be further modified with Cu‐complexes to form a fullerene‐like cluster based zigzag chain (Cu‐V30Nb12).