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In this work, aluminum nitrate (Al(NO3)3), active carbon and C12H22O11 were used as raw materials. The nano aluminum nitride powders (AlN) were synthesis by polymer network method. Aluminum nitride (AlN) exhibits high thermal conductivity, low dielectric permittivity and good electric insulativity. It has a very high synthetic temperature, however, results in a high cost. The aim of this investigation is to develop a new method of fabricating ultra-fine AlN powders to lower the synthetic temperature of AlN. The influences of different carbon sources and the synthetic temperature on fabricating AlN powders via polymer network method were investigated, and the mechanism of AlN formation was also identified. The results indicated that as using sucrose (C12H22O11) as the carbon source, the optimum synthetic process condition for fabricating ultrafine AlN powders was at 1500 °C for 2 h. Comparing with the mechanical ball-milling method, the temperature of synthesizing AlN powders was lowered about 100 °C. Furthermore, the size of as-synthesized AlN was finer from 50 nm to 80 nm.