A novel three-step technique was employed to synthesize the well-distributed AlN nanopowders. First, the hollow spherical precursor particles with an average diameter of 2–5 μm, consisting of an amorphous structure mixture of Al2O3 and C, was prepared by carbon-containing droplet combustion method by using glucose, urea, and aluminum nitrate as starting materials. The carbothermal reduction and nitridation (CRN) was carried out at 1500◦C under N2 flow for 2 h and subsequently the CRN product was calcined at 700◦C in air for 1 h to remove residual carbon and transform the CRN product to high-purity AlN powders consisting of nanostructured hollow spheres. The formation mechanism of precursor and AlN hollow spheres was discussed in detail. The AlN powder exhibited well-distributed spherical particles with a size of 30–50 nm and good sinterability. After additive-free and pressureless sintering at 1800◦C for 2 h, the relative density of the sintered AlN sample was measured to be 99.02%. [ABSTRACT FROM AUTHOR]