Poly(vinyl alcohol) (PVA) and titanium dioxide (TiO2) composite films were prepared by gelation/crystallization from a dispersed solution containing different TiO2 contents against PVA. Iodine was incorporated into the composites, and the iodine-incorporated composites were carbonized under argon gas in the temperature range of 700-1600 degrees C. Under the carbonization process, the incorporation of iodine into composites ensured tough films without cracks. This indicated that iodine incorporation played ail important role as a catalyst to promote the formation of cross links between amorphous carbon chains through the resultant Ti-C structure that occurs by hydration. Surprisingly, X-ray diffraction intensity measurements revealed that the coagulated TiO2 powders in the composite film carbonized at 1200 degrees C remained predominantly anatase type, which has generally been known its photocatalytic activity. The perfect transition to the rutile-type structure dramatically occurred at 1600 degrees C. Judging from the carbon coating on the TiO2 particle surface as detected by ESCA, no disruption of the composite was found to be due to the appearances of TiO3 groups and the Ti-C structure performing cross linking between neighboring amorphous carbon chains. The characteristics of anatase-type TiO2 crystallites and amorphous carbon structures were analyzed using the para-crystalline theory concerning the distance fluctuation between graphene sheets, The electrical conductivity of the carbonized composite was ca. 0.01 S/cm and was independent of the TiO2 admixed in the carbon matrix.