A series of enone-hydrazones were synthesized through the reaction of enaminones with hydrazones under solvent-free, additive-free, and metal-catalyst-free conditions. The target products were obtained in high yields, with outstanding group tolerance, stereoselectivity, and chemical selectivity. In this work, a series of novel enaminone skeleton compounds were synthesized, and deuteration experiments showed that enone-hydrazones have different properties from traditional electron-deficient enketones.