We synthesized one dimensional (1-D) AlN whiskers by using the cobalt oxide catalyst-assisted carbothermal reduction method. The formation of AlN whiskers is investigated by the thermo-gravimetric and differential thermal analysis, Fourier-transformed infrared spectra, X-ray diffraction patterns, scanning electron microscopy and transmission electron microscopy observations. It was found that Co₃O₄ droplets on the surfaces of Al₂O₃ acted as a catalyst for the growth of AlN whiskers by vapor-liquid-solid (VLS) mechanism. In addition, AlN whiskers/PVA composites aligned in parallel with the heat flow direction showed an excellent thermal conductivity about three times higher than those of the perpendicularly aligned whisker composites.