A highly efficient and simple procedure for the synthesis of substituted benzenes is described. A range of aryl and alkyl ketones were used to conduct triple condensation reactions in the presence of a catalytic amount of nano-Al2O3/H5PW10V2O40 as an efficient and recyclable catalyst under solvent-free conditions. The supported heterogeneous catalyst was characterized using SEM, XRD, DLS, UV-Vis and FT-IR spectroscopy. All condensation reactions were completed in a suitable time compared to existing methods without formation of any undesirable 1,2,4-trisubstituted by-products. The entire synthetic sequence is cost-effective, environmentally benign, and possesses convenient generality, which makes the method meritorious as a valid contribution to the existing methods in the field of highly substituted benzene synthesis