NH 4 ) 42 [Mo 72 VI Mo 60 V O 372 (CH 3 COO) 30 (H 2 O) 72 ], a Keplerate-type giant nanoporous isopolyoxomolybdate, denoted as ({Mo 132 }), was found to have extraordinary catalytic activity in the synthesis of 1,8-dioxo-octahydroxanthenes, and 1,8-dioxodecahydroacridines via one-pot reactions. The catalyst was prepared using inexpensive and readily available materials and characterized using FT-IR, and UV spectra. The desired products were obtained only within a few seconds in high yields under solvent-free conditions at 130°C. Furthermore, the procedures and work-ups were simple and the catalyst can be conveniently recovered and reused. To our knowledge, the catalyst exhibits the highest activity over other procedures available in the literature for the synthesis of the mentioned compounds.