A regioselective, solvent-free and catalyst-free synthesis of isoxazoles has been successfully developed under ball milling conditions. Milling the mixtures of N-hydroxybenzimidoyl chlorides and enamino carbonyl compounds in a ball mill at a frequency of 14.6?Hz for 20–60?min afforded isoxazoles in up to 86% yields. A possible reaction mechanism leading to the formation of the observed isoxazoles is proposed.