As starting materials, tetraethyl orthosilicate, resorcinol and formaldehyde were used to prepare a distinctive composite film of SiO2/C two-phase interpenetrated porous nanostructures on the surface of carbon foil ((SiO2/C)@Cf) when the mixed polymerizations (condensations) on the surface of graphene oxide and subsequent heat treatment were carefully manipulated. The microstructures of as-prepared films were characterized by FESEM, TEM, EDS element mapping, BET, etc and their charging/discharging behaviors and electrochemical impedance spectra were quantitatively analyzed. It has been found that (SiO2/C)@Cf shows extraordinary capacity enhancement featured with excellent cycling capacity and rate performance as anode materials of Li-ion batteries, such as 1274 mAh g−1 after 2000 cycles at 1 A g−1 and 463.5 mAh g−1 at 5 A g−1, in comparison with the layered SiO2/C composite films. More interestingly, the CV curves of (SiO2/C)@Cf before and after 2000 cycles of charge/discharge evidently shows a remarkable initial pseudo-capacitive capacity and its unusual enhancement with increasing number of cycles, which should be attributed to the small size effect of SiO2 domains embedded in carbon phase and their gradual refinement, leading to an increase in the effective electrochemical reaction area and apparent diffusivity of Li-ions.