Covalent grafting of heteropolyanions hybrids B,α-[AsIIIW9O33{P(O)(CH2CH2CO2H)}2]5- on 3-aminopropyle functionalized SBA-15 has been achieved through the formation of peptide bonds. The covalent link has been confirmed by using IR and 13C CP MAS NMR spectroscopies. Electrostatic interactions between carboxylate and protonated amines have been discarded on the basis of the retention of POMs after repeated washings of the resulting material by ionic liquid (bmimCl). This is the first example of anchored monovacant polyoxometalates (POM) in which nucleophilic oxygen atoms are still available after incorporation into mesoporous supports. Further characterization of the textural properties of grafted materials has shown that they still retain an important mesoporosity, which is compatible with their potential use in heterogeneous catalysis. Such systems are thus interesting candidates for the preparation of anchored homogeneous catalysts in which the POMs would play the role of polydentate inorganic ligands for the active centers.