The extent of poly epsilon-caprolactone (PCL) incorporation into silica networks prepared by the sol-gel process depends on the HCl:tetraethoxysilane (TEOS) molar ratio and the H2O:TEOS molar ratio, as well. The PCL incorporation increases with the concentration of the acid used as the catalyst. Dynamic mechanical analysis (DMA) indicates that increasing the acid concentration or decreasing the water content results in a higher glass transition temperature for the organic component in the hybrid materials, whereas the modulus does not change significantly. Small-angle X-ray scattering (SAXS) data agree with a nanoscopic phase separation of the two constitutive components: the organic polymer and the silica network. The characteristic length of this two-phase structure increases with acid content (except for the lower HCl:TEOS molar ratio of 0.05) and with water content (except for the higher H2O:TEOS molar ratio of 2.0). The structure of the PCL/SiO2 interface is mass fractal and the structure is more open when the acid content is lower or the water content higher.