Two kinds of rare earth (RE) complexes were intercalated into zirconium bis(monohydrogenphosphate) (α-ZrP) by exchanging the RE complexes into the p-methyoxyaniline (PMA) preintercalated compound Zr(O3POH)2·2PMA (α-ZrP·2PMA). Powder X-ray diffraction patterns reveal that Eu(DBM)3phen (DBM: dibenzoylmethane, phen: 1,10-phenanthroline) and Tb(AA)3phen (AA: acetylacetone) intercalated into α-ZrP·2PMA. This was confirmed by the UV-visible spectra of both the RE complexes and the assemblies. At the same time, the assemblies have better luminescent properties, and the fluorescent lifetimes of RE3+ in the excited state in the assemblies are much longer than those in the complexes. The stabilities of the assemblies under UV radiation are much better than those of the RE complexes.