A multicomponent cascade cyclization reaction using aryl methyl ketones, aryl amines, and enaminamide reagents to construct 3‐hydroxy‐1H‐pyrrolo[3,4‐b]quinolin‐1‐one skeleton with good substrate compatibility (50 examples) has been reported. The one‐pot, metal‐free process formed two C‐C bonds, two C‐N bonds, and a tetrasubstituted carbon stereocenter containing a hydroxyl group. The reaction enabled modified transformation of drug molecules and derivatization of products.