The role of molecular receptors in aqueous biphasic hydroformylation of higher olefins is highlighted through a detailed analysis of their molecular recognition properties. The behavior of cyclodextrins and calixarenes as molecular receptors is especially emphasized and discussed. Their supramolecular interactions with the substrates and the water-soluble ligands proved to be an essential parameter guiding the reaction performances. The hydroformylation activity and chemo- and regio-selectivities can thus be accurately controlled by a suitable match between the receptor and the reaction components. Development outlooks are also presented.