Metal-organic framework MIL-53(Fe) (MIL = Materials of Institute Lavoisier) as recyclable and heterogeneous catalyst efficiently catalyzed the synthesis of 2-Aryl-1H-Benzimidazole derivatives from o-phenylenediamine and aldehydes in solvent-free condition. This method provides benzimidazole in good to excellent yields with little catalyst loading. Furthermore, the catalyst can be readily isolated by filtering and no obvious loss of activity was observed when the catalyst was reused in five consecutive runs.