A porous heteroatom-rich Cd(II)-polymeric framework which is generated from an ethylene glycol ether-bridging dicarboxylate ligand L, 4,4'-bipy and Cd(II) ion is reported. It contains one-dimensional tubes (9-11 angstrom) which are able to trap cationic lanthanide hydrates such as Eu(H2O)(8)(3+), Tb(H2O)(8)(3+), and Nd(H2O)(8)(3+) under ambient conditions to generate Ln(H2O)(8)(3+)-loaded materials. In addition, the heteroatom-rich host material can effectively protect and sensitize the encapsulated Ln(3+) emitters in their hydrate form in both air and aqueous media. Furthermore, the dual- and bimodal-emissions are successfully realized by intercalation of the different Ln(3+)-hydrates based on a guest-driven approach.