Four alkoxohexavanadate-based Pd-POVs [Pd(dpa)(acac)](2)[V6O13(OMe)(6)] (1), [Pd(dpa)(acac)](2)[V6O11(OMe)(8)] (2), [Pd(dpa)(acac)](2)[V6O11(OMe)(8)].H2O (3), and [Pd(DMAP)(2)(acac)](2)[V6O11(OMe)(8)].H2O (4) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; DMAP = 4-dimethylaminopyridine; acac = acetylacetone anion) have been synthesized and fully characterized by single crystal X-ray diffraction and powder X-ray diffraction analyses, Fourier transform infrared spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In 1-4, Pd complexes and hexavanadate anions are assembled through electrostatic interactions. Interestingly, the [V6O11(OMe)(8)](2) cores in 2 and 3 are a pair of isomers that can be isolated by controlling crystallization temperature. Moreover, to the best of our knowledge, the {V6} core in 3 represents a new octamethoxyhexavanadates cluster. It is notable that compounds 1-4 exhibit excellent heterogeneous catalytic performance in the oxidation of benzyl-alkanes with t-butylhydroperoxide as oxidant. Among them, the catalytic activity of 1 (conv. and selec. up to 99%, respectively) outperforms others and can be reused without losing its activity.