The polycrystalline mullite fiber was synthesized from various combination of starting materials including metal alkoxides and colloidal sol by the sol-gel process. The best spinnability was observed in the sol which showed shear thinning and hysteresis (i.e., thixotropic flow), indicating that the network structure was broken down as the shear rate increased. The mullite fiber was polycrystalline after firing and characterized by thermal analysis, XRD, FT-IR spectroscopy, rheological measurements, and SEM.