Coordination of vanadyl (VO2+) ions with 8-hydroxyquinoline (8Hq) in the interlayer space of layered silicate magadiite (mag) was realized by solid-solid intercalation. Composition, structure and morphology of this compound were studied by X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The obtained results indicate that the basal spacing of decorated mag increased after intercalation and suggest that VO-8Hq decorated into the interlayer of mag (VO-mag-8Hq) was successfully synthesized for the first time. Optical properties of VO-mag-8Hq were studied by ultraviolet-visible (UV-Vis) and photoluminescence spectroscopy (PL). The findings reveal that VO-8Hq complexes in the interlayer space exhibit extraordinary fluorescence properties and the confined space of mag influences the optical properties of VO-8Hq complexes.