Nanostructured SiO2–H2SO4 as an efficient and nano catalyst for one-pot synthesis of phtahalazines via three-component condensation of an aromatic or aliphatic aldehyde, malononitrile and 5-amino-2,3-dihydro-phthalazine-1,4-dione. Nanostructured SiO2–H2SO4 was synthesized and characterized via FT-IR and SEM techniques. It is rapid and efficient catalyst for one-pot synthesis of the biologically important 3,9-diamino-5,10-dioxo-1-aryl-5,10-dihydropyrazolo[1,2-b]phthalazine-2-carbonitrile derivatives. The significant features of this methodology are nontoxic catalyst, short reaction time (10 min), recyclability, low catalyst loading, green organic solvent (ethanol), and avoiding tedious purification step.