Two organic-inorganic hybrid compounds, (Bu4N)2[Mo6O18(NAr)] (Ar = 2-CH3-4-BrC6H3 (1) or 2,6-CH3-4-BrC6H2 (2)) have been synthesized via the DCC dehydrating protocol of the reaction of [α-Mo8O26]4- with 2-methyl-4-bromoaniline hydrochloride or 2,6-dimethyl-4-bromoaniline hydrochloride in anhydrous acetonitrile, which have been characterized by UV-Vis spectra, 1H NMR, IR, cyclic voltammetry and X-ray single-crystal diffraction study. Both compounds crystallize in the monoclinic space group P over(1, ̄), which are featured in a terminal phenyli...