Nowadays it is necessary to develop selective sensing materials of ammonia and amines because toxic ammonia and amines are widely distributed in the environment. In this work, π-electron-deficient N,N′-di(4-pyridyl)-1,4,5,8-naphthalene diimide ligand was used to construct coordination polymers with selective sensing behaviors towards electron-rich ammonia and amines vapors. Three coordination polymers 1–3 with solvents dependent entanglement structures have been successfully synthesized. Compounds 1 and 3 display similar 2D + 2D → 3D polycatenation architectures, but they have pores with different sizes that can accommodate different lattice solvent molecules. Compound 2 exhibits a 3D 2-fold interpenetrating framework with a 6-connected pcu net. Compounds 1 and 3 can selectively sense ammonia and amines vapors in solid state through visual color changes with different response time.