The growth of well-aligned AlN nanorods with hairy surface by a vapor-solid (VS) process was studied. The well-aligned AlN nanorods with hairy surfaces provide a new hierarchical nanostructure and serve as a promising candidate for FE emitters because of their low electron affinity and the geometry of the multiple-nanotip surfaces. The AlN nanostructures were characterized by transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). Intensive light emission from AlN materials has been observed. The hierarchical AlN nanostructures have potential applications in optoelectronic and FE nanodevices.