I this work, electrospinning was used for synthesis of fiber with small diameter and high homogeneity. Precursor sol was prepared from aluminum isopropoxide (AIP), hydrated aluminum nitrate (AN) as the alumina sources and tetraethylorthosilicate (TEOS) as the silicon source, and then mixed with polymeric solution, which contains different proportion of polyvinyl alcohol (PVA, as the template). Then synthesized nanofibers sintered at different temperatures in calcination and microwave furnace. The details of crystal development, microstructure and thermal decomposition behavior of the electrospun nanofibers were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). According to the results, sintered samples via microwave furnace had higher thermal stability and the crystallization temperature was lower than those sintered in calcination furnace.