The novel biodegradable poly(epsilon-caprolactone)/titanium dioxide hybrid materials were prepared via in situ sol-gel process of tetrabutyl titanate (TBT) as inorganic precursor in the presence of PCL. The relationships between morphology, microphase separation, crystalline structure, and properties were investigated by means of XPS, SEM, XRD, DSC, and in vitro degradation test. The microstructures of the bulk hybrids display two-phase microscopic separation on the nanometer scale, which domain is 20-80 nm. The surface morphology and intermolecular bonding interaction are significantly dependent on inorganic component. The relative crystalline degrees of PCL/TiO(2) hybrid nanocomposite materials were controlled by both inorganic component and hydrogen bonding special interaction. The hybrid nanocomposite materials with TiO(2) showed faster biodegradation rate than that of pure PCL itself, and the transparency corresponding to microstructure increase with increase of inorganic component content.