An efficient and reusable catalytic system for aerobic oxidation of alcohols and one-pot synthesis of benzimidazoles from alcohols with ceric ammonium nitrate and PEG 1000 -ionic liquid-immobilized 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is described. This system shows excellent activity and selectivity, affording the target products with good yields. Moreover, the catalytic system can be recycled and reused without significant loss of catalytic activity after seven runs.