A series of N-heteroaryl formamides were efficiently synthesized from heteroarylamines and formic acid using Al2O3 nanoparticles as a heterogeneous catalyst under solvent-free conditions. The smaller size of Al2O3 nanoparticles with a higher surface to volume ratio has a promising catalytic activity, resulting in a short reaction times and high reaction yields under mild reaction conditions. The catalyst could be recycled and reused four times without a noticeable decrease in its activity.