A multicomponent synthesis of β‐enaminones is explored using nitroalkane as a reagent and a solvent. The one‐pot reaction of 1,3‐diketone, aldehyde, and amine using nitromethane as the solvent resulted β‐enaminones exclusively. When the same reaction was performed in nitroethane, however, lactone ring‐opening of coumarin moiety was observed, leading to the formation of hydroxy‐β‐enaminones. The possible mechanisms for these reactions are deduced and the substrate scope of the reaction is investigated.