A series of structurally well-defined enantiopure tripodal allyl dendritic structures bearing three amine groups have been synthesized. The hydrogenation of the allyl groups in the presence of a Pd/C catalyst gave the corresponding enantiopure n-propyl counterparts. Treatment of these n-propyl amino dendrimers with heteropolyacid H3PW12O40 and excess H2O2 gave the enantiopure n-propyl {PO4[WO(O2)2]4}3– salts. Characterization of these dendritic POM hybrids in solution by NMR spectroscopy, elemental analysis, UV/Vis spectrophotometry, circular dichroism (CD), vibrational circular dichroism (VCD) and fluorimetry indicates the presence of POM–ligand interactions and confirms their optical and chiroptical properties. The hybrid compounds selectively oxidized sulfides to the corresponding chiral sulfoxides with up to 13 % enantiomeric excess (ee), highlighting the transfer of chirality from the dendritic wedges to the inorganic cluster. The properties of the POM anion, especially its solubility and regio- and stereoselectivity, are sensitive to the structure of the cation. The catalyst was recovered by precipitation without any discernible loss in activity, selectivity or enantioselectivity over three catalytic cycles at –50 °C. Interestingly, a dendritic effect was noted in the enantioselectivity as the dendritic-POM hybrids are more selective than their non-dendritic counterparts. The ee resulting from chirality transfer to the anionic POM unit is comparable to that obtained in our previous work with monopodal dendritic polyoxometalates (14 %) despite the polyvalency of the highly charged tripodal ligand, which is rationalized by different spectroscopic methods.