The nanostructures of the cross-linked hybrid (X-ASiO-PVPNP) films were first investigated by employing synchrotron radiation grazing incidence X-ray diffraction (GIXD) techniques. As shown in the 2D GIXD images (Fig. 3a), very weak (almost unrecognizable) Debye diffraction ring was measured for the pristine ASiO films (PVP content = 0 wt.%), while no particular diffractions were measured for the pristine PVP films. Interestingly, an intense Debye ring was measured for the cross-linked hybrid (X-ASiO-PVPNP) films with 5 mol.% PVP. The similar strong Debye ring was also measured for the hybrid films with 10 mol.% PVP. Based on the scattering vectors for the Debye rings, the d-spacing (d) values calculated were in the range of 0.62~1.57 nm. The detailed investigation with the 1D GIXD profiles (Fig. 3b) disclosed that the intense Debye rings have a maximum peak at around qxy = 0.66 Å−1 (2θ = 6.75°), leading to d = 1 nm, in the directions of both out-of-plane (OOP) and in-plane (IP). Considering the GIXD results, it is shortly concluded that the addition of PVP had a strong influence on the reorganization (recrystallization) of VTES molecules.