In this manuscript, the synthesis and X-ray characterization of a new decavanadate complex, [H2L1]2[HL2]2[V10O28], is reported, where [H2L1] and [HL2] are the protonated forms of ligands L1 and L2 [L1 = 4-(2-aminoethyl)morpholine and L2 = N-ethylidene-2-morpholinoethanamine]. H-bonding interactions between the bridging oxygen atoms of the anion and the ammonium groups (N+–H···O) of the ligands are selectively formed. Moreover, a multitude of CH···O interactions are also established between the counter ions. DFT calculations have been used to rationalize the interactions observed in the solid state and to compare the relative importance of the charge assisted NH···O H-bonds with the CH···O ones, evidencing that almost 40 % of the interaction energies are due to CH···O contacts. Moreover, using MEP surface calculations, the H-bond acceptor ability of the different O-atoms of [V10O28]6- anion has been studied. To our knowledge, such analysis is unprecedented in the literature.