The intercalation of Tb(III) into layered magadiite is achieved by three-step ion exchanges with H+/Na+, TBA+ (tetra-n-butylammonium ions)/H+ and Tb(EDTA)3+/TBA+. Various techniques, including powder X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray (SEM-EDX), thermogravimetric and differential thermogravimetry (TG-DTG), Fourier transform infrared (FTIR) spectroscopy, and photoluminescent spectroscopy (PL), were employed to characterize the Tb-intercalated magadiites. The XRD results revealed that the basal spacing of the Tb-intercalated magadiites was obviously larger than that of the Na-magadiite, confirming the intercalation. The IR spectra showed no bands attributable to EDTA in the Tb-intercalated magadiites, indicating that the EDTA has broken away from Tb(III)-ETDA complexes during ion exchange. Moreover, the basal spacing of Tb-intercalated magadiite tends to increase slightly with the increase in water content in the Tb-intercalated magadiite. The PL spectra show weak emissions, attributed to 5D4-7FJ (J = 3, 4, 5, 6) transitions of Tb3+.