Nano scaled mullite (3Al2O3·2SiO2) powders had been fabricated by an organic-inorganic solution technique using a polyvinyl alcohol (PVA) as an organic carrier. PVA polymer contributed to a soft and porous powder microstructure, and ball milling with the porous powder was effective in making nano-sized mullite powders. In addition, the degree of polymerization of PVA affected the crystallization behavior. The fully crystallized and ball-milled mullite powders had an average particle size of 120 nm with a specific surface area of 67.0 m2/g. In this paper, the simple solution technique and milling process for the fabrication of nano scaled mullite powders are introduced. And the effects of PVA on the crystallization behavior and powder specific surface area are also studied. The characteristics of the synthesized powders are examined by using XRD, TEM, particle size analyzer and nitrogen gas adsorption.