Members of the layered rare-earth hydroxides (LRHs) family with the generalized formula (Y(1-x)Ln(x))(2)(OH)(5)NO(3)·nH(2)O (Ln = Tb, Eu; 0% ≤x≤ 100%) (named as YTb-LRHs, YEu-LRHs) have been synthesized via a hydrothermal route. Crystal structures and elemental compositions have been investigated by X-ray diffraction (XRD), elemental analysis, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). These results show that Ln(3+) species are successfully incorporated into the LRH host lattice to form layered hydroxide solid solutions. The YTb-LRHs and YEu-LRHs samples exhibit well-defined photoluminescence. The color of the luminescence can be tuned by changing the concentration of Ln(3+). Furthermore, the ternary YTbEu-LRH system was also synthesized, an example of the host layers containing variable types of the lanthanide cations. This provides the possibility to tune the chemical composition and the luminescent properties of the lanthanide species with the flexibility of intercalation hosts for potential applications in luminescent materials and field emission displays.