This paper reports a series of novel metal acetylacetonates covalently anchored onto amine functionalized silica/starch composite, prepared by the Schiff condensation of metal acetylacetonates [Co(acac)(2), Cu(acac)(2), Pd(acac)(2), Ru(acac)(3), Mn(acac)(3), Co(acac)(3)] with organically modified 3-aminopropyl silica/starch composite. Different metal acetylacetonates have been chosen with a view to select the most active heterogeneous catalyst. Among various catalysts, covalently anchored Cu(acac)(2) onto amine functionalized silica/starch composite [ASS-Cu(acac)(2)] was found to be the most active and recyclable catalyst for the one-pot thioetherification and one-pot three component synthesis of 2H-indazoles via consecutive C-N and N-N bond formations. All the catalysts were characterized by FTIR, TGA and AAS analysis and the most active catalyst, [ASS-Cu(acac)(2)] was further characterized by SEM and TEM. The catalyst could be recovered by simple filtration and reused with almost consistent activity for four consecutive runs.