We report a novel Nb(V)−carboxylate cluster obtained from reaction of niobium(V) ethoxide and pivalic (trimethylacetic) acid. Single crystal X‐ray diffraction data reveal a structure composed of 16 Nb(V) ions featuring oxo‐, ethoxy‐ and pivalate moieties. The new cluster exhibits the highest nuclearity among structurally characterized niobium carboxylates reported to date.