A novel host–guest approach to synthesize the hybrid AlPO 4 /nano-carbon (graphite-like) (AlPO 4 /NCG) material, in which it is composed of two steps: a hydrothermal synthesis of a new layer-structured AlPO 4 /Benzylamine and the preparation of AlPO 4 /NCG by calcinations at 873K using this layer-structured material as precursor, was firstly presented. The layered structure of AlPO 4 /Benzylamine was verified by X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements, with a layer distance of 1.95nm. And the layer-structured AlPO 4 /Benzylamine after calcinations was confirmed to be AlPO 4 /NCG via X-ray photoelectron spectroscopy (XPS) and Raman spectra measurement.