Sodium hydroxide catalyzed a new multicomponent reaction of salicylaldehydes, malononitrile and cyanoacetamides under ‘on-water’ conditions, which results in the facile and efficient formation of the corresponding substituted 2-amino-4H-chromenes in 80–95% yields. The convenient approach to the substituted 2-amino-4H-chromenes developed here — the promising small-molecule ligands for different biomedical applications with known spasmolitic, diuretic and antianaphylactic activities — is beneficial from the viewpoint of diversity-oriented large-scale processes and represents a fast, efficient and environmentally benign ‘on-water’ synthetic concept for multicomponent reactions strategy.