AlN whiskers have been successfully synthesized by carbothermal reduction. The thermodynamics and growth kinetics of AlN whiskers were studied at 1600°C using CaCO3 as a catalyst. The research indicated that AlN whiskers are more easily nucleated from the liquid phase than at the surface of solid phase. AlN whiskers are nucleated by VLS mechanism and the liquid, which plays a dominant role in the VLS mechanism, is formed by Al-Ca interphases, such as CaO×2Al2O3 and CaO×6Al2O3. Kinetic studies suggest that the catalyst reacts with Al2O3 to form a low melting point eutectic (1390°C). The liquid phase formed at this low melting point eutectic provides good conditions for nucleation of AlN whiskers. At the synthesis temperature, the liquid phase vaporizes, thus creating suitable conditions for the subsequent growing of whiskers by the VLS mechanism. This growing mechanism conforms to thermodynamics and a lot of proof indicates that screw dislocations play an important role in the process of the whiskers' formation.