NiO nanoparticles were assembled on the surface of palygorskite (PAL) nanofibers to produce NiO/palygorskite (NiO/PAL) composites via electrostatic attraction. The samples were characterized by thermogravimetric-differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), Brunauer-Emmet-Teller (BET), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). The interfacial characteristics between NiO nanoparticles and PAL nanofibers were in detail investigated. The PAL nanofibers were uniformly decorated with well-dispersed crystalline NiO nanoparticles with an average size of 8 nm. The results further indicated that the interfacial binding of NiO and PAL fiber ensured the stable composite structure of NiO/PAL. The NiO/PAL composites exhibited higher photocatalytic activity than pure NiO for methyl orange photo-degradation under UV-light. The as-synthesized nanocomposites showed an interesting potential application in the environmental fields. (C) 2012 Elsevier Inc. All rights reserved.