A facile NiO–SiO 2 mixture intercalated clay with ordered porous structure was assembled via a novel intregallery interfacially controlled functionalization method is successfully established. The starting mesostructured silica-pillared clay is assembled by intragallery ammonia-catalyzed hydrolysis of tetraethoxysilane using cationic surfactant as gallery template, and subsequently, the formed porous clay precursor is combined with nickel–ammonia complex to obtain intragallery interfacially controlled functionalization of nickel oxide. The kind of structural transformation has been confirmed by elemental analyses, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), N 2 adsorption–desorption isotherms, DR UV–vis absorption spectra, temperature-programmed reduction (TPR), X-ray photoelectron spectrometer (XPS) and transmission electron microscopy (TEM). The results elucidate that most of the grafted nickel species was combined with Si–OH on the surface of gallery pores and other was incorporated into tetrahedral sites in the intragallery silica framework. The effect of in situ combined nickel–ammonia complex with porous clay precursor is an essential factor to direct the formation of the intragallery interfacially controlled functionalization. And the porous surface Si–OH takes the role decision for the functionalization process. By changing the concentration of nickel–ammonia complex during synthesis, the porous structure, surface area and scattering domain size is effected. Furthermore, the obtained solid materials exhibit excellent selective adsorption for thiophene from coking benzene. The formation mechanism of intragallery interfacially controlled functionalization is proposed.