TiO2/ Poly(styrene maleic anhydride) nanocomposites were synthesized In situ via multi-component solution method. It was found that the composites existed in the formation of covalent bonding between TiO2 and polymer by infrared spectra. The systematical morphology change of TiO2 in the composites with different reaction conditions was observed through transmission electron microscope. Based on the mechanism of " anchor wrapping ", the nanocomposites were in the form of three-dimensional net with the separated nano-crystalline TiO2 micro-phases inside, and the aggregation of TiO2 grains was successfully inhibitted. The anatase phase of TiO2 was proved by X-Ray diffraction.