A direct ion-exchange approach was adopted to intercalate ionic lanthanide complexes into layered α-zirconium phosphate. The obtained luminescent hybrid composites were characterized via Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and photoluminescence spectroscopy. These composites exhibit an expanded layer distance as well as higher thermo- and photo-stability. Moreover, a simple, effective and robust luminescent sensor has been developed based on the aforementioned composites for detecting organic amines, with high selectivity and sensitivity.