In vitro influence of five synthesized functionalized hexavanadates (V 6) on commercial porcine cerebral cortex Na + /K +-ATPase activity has been studied. Dose dependent Na + /K +-ATPase inhibition was obtained for all investigated compounds. Calculated half maximal inhibitory concentration IC 50 values, in mol/L, for Na + /K +-ATPase were 7.6 × 10 −5 , 1.8 × 10 −5 , 2.9 × 10 −5 , 5.5 × 10 −5 for functionalized hexavanadates (V 6) with tetrabutylammonium (TBA) [V 6 –CH 3 ][TBA] 2, [V 6 –NO 2 ][TBA] 2 , [V 6 –OH][TBA] 2 and [V 6 –C 3 ][TBA] 2 respectively. [V 6 –OH][Na] 2 inhibited Na + /K +-ATPase activity up to 30% at maximal investigated concentration 1 × 10 −3 mol/L. This reactivity has been interpreted using a study of the non-covalent interactions of function-alized hexavanadate hybrids through Cambridge Structural Database (CSD) analysis. Bibliographic searching has led to 18 different structures and 99 contacts. We have observed that C–H⋯O contacts consolidate the structures. We have also performed density functional theory (DFT) calculations and have determined electrostatic potential values at the molecular surface on a series of functionalized V 6. These results enlightened their chemical reactivity and their potential biological applications such as the inhibition of the ATPase.