The fully oxidized Lindqvist-type hexavanadate compounds decorated by phosphine-derivatized Au(I) moieties oriented in a transoid fashion (n-Bu4N)2[V6O13{(OCH2)3CCH2(N3C2C6H5)AuP(C6H4OMe)3}2] (POMNAu) and (n-Bu4N)2[V6O13{(OCH2)3CCH2OCH2(C2N3H)AuP(C6H4OMe)3}2] (POMCAu) have been prepared by azide–alkyne cycloaddition reactions and characterized by various techniques, including NMR, IR, and UV/vis spectroscopy and electrospray ionization mass spectrometry. Electronic structure calculations unveil the potential of these model hybrid junctions for application in controlled charge-transport experiments on substrate surfaces.