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Large quantities of high-quality, ultra-long hexagonal crystal structure AlN whiskers with diameters from 1 to 3 μm and lengths up to several millimeters were grown by physical vapor transport method in the temperature of 1800℃.The whiskers are characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), high-resolution transmission electron microscopy (HRTEM), and photoluminescence spectra (PL).SEM analysis shows that no liquid drops at the end of the whiskers, indicating that the growth mechanism of the whiskers might be regarded as a vapor-solid (VS)mechanism.