Herein, we report for the first time the aldol reaction of a wide range of α‐ketoamide with α,β‐unsaturated ketone via the activation of potassium hydroxide in aqueous medium. The protocol provides a straightforward and atom‐efficient strategy for the synthesis of a new family of multifunctional α‐hydroxy amides contain α,β‐unsaturated ketone group from easily accessible substituted α‐ketoamide and α,β‐unsaturated ketone. The reaction features mild reaction conditions, green solvent, one of which is quaternary carbon substitution. The method can accommodate various substituents and substitution patterns, afford the products up to 95 % yields.