A liquid-solid metathetical reaction method (LSMRM) of synthesizing AlN nanocrystallines is presented. AlN nanocrystallines made through LSMRM are characterized by X-ray diffractions (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Fourier transformation infrared (FT-IR) spectroscopy, and Raman spectroscopy. The results show that the samples are single hexagonal-phase AlN and the size of the AlN samples is about tens of nanometer.