Nanostructured α-Fe_2O_3 were prepared by precipitation followed by calcination method.Cetyltrimethylammonium bromide(CTAB) was used as surfactant.The nano α-Fe_2O_3 was then silanized with(3-chloropropyl)-triethoxysilane(CPTES) by room temperature mixing of α-Fe_2O_3 and CPTES to produce silane coated α-Fe_2O_3(ClPr-Si@Fe_2O_3).As-synthesized ClPr-Si@Fe_2O_3 was functionalized via covalent grafting of benzimidazole to produce 3-(l-benzimidazole)Pr-Si@Fe_2O_3.This was further reacted with bromine to afford α-Fe_2O_3 immobilized benzimidazolium tribromide(α-Fe_2O_3-BIM tribromide).This ionic liquid(IL)α-Fe_2O_3 BIM tribromide was characterized by FT-IR,XRD,TEM,SEM,TGA,VSM,EDX and BET analysis.The as-synthesized IL tribromide was used as catalyst for one-pot synthesis of highly substituted piperidines.The method is greener in terms of solvent selection,recovery of the catalyst and efficiency. Nanostructured α-Fe_2O_3 were prepared by precipitation followed by calcination method. Cetyltrimethylammonium bromide (CTAB) was used as surfactant.The nano α-Fe_2O_3 was then silanized with (3-chloropropyl) -triethoxysilane (CPTES) by room temperature mixing of α-Fe_2O_3 and CPTES to produce silane coated α-Fe_2O_3 (ClPr-Si @ Fe_2O_3) .As-synthesized ClPr-Si @ Fe_2O_3 was functionalized via covalent grafting of benzimidazole to produce 3- (l-benzimidazole) Pr_Si@Fe_2O_3.This was further The ionic liquid (IL) α-Fe_2O_3 BIM tribromide was characterized by FT-IR, XRD, TEM, SEM, TGA, VSM, EDX and BET analysis. The as-synthesized IL tribromide was used as catalyst for one-pot synthesis of highly substituted piperidines. The method is greener in terms of solvent selection, recovery of the catalyst and efficiency.