A catalyst‐free approach has been introduced for the conjugate addition of aromatic amine nucleophiles to α, β‐unsaturated N‐methyl maleimide under microwave irradiation by utilizing water as a promoter. Catalyst‐free, environmentally friendly, short‐reaction time, green solvent, and mild reaction conditions are the advantages of this protocol. This reaction provided good to excellent yields with aromatic anilines as nucleophiles. The benefits of this reaction align with the principles of green and sustainable synthetic chemistry, making it widely applicable in organic synthesis and pharmaceutical chemistry.