A practical and environmentally benign cascade multicomponent condensation of naphthol/thionaphthol/naphthylamine, formaldehyde, and DBU in water without any catalysts has been achieved. A wide variety of dihydrooxazine, dihydrothiazine, and tetrahydrobenzoquinazoline derivatives N-substituted with a tether bearing a caprolactam unit were afforded in moderate to good yields. The advantages of being cost-effective, metal-free, and easily handled and the use of water as medium made this protocol conform with the principle of green synthesis.