Over the past ten years, understanding the self-assembly process within mesostructured silica films has been a major concern. Our characterization approach relies on two powerful and complementary techniques: in situ time-resolved FTIR spectroscopy and ex situ solid-state NMR. As model systems, three silica/surfactant films displaying various degrees of mesostructuration were synthesized using an amphiphilic block copolymer (PEO-b-PPO-b-PEO) via a UV light induced self-assembly process. The key idea is that the hydration state of the hydrophobic PPO chain is expected to be different depending upon whether the sample is amorphous (blend) or mesostructured (segregated). With real-time FTIR experiments, we show that the methyl deformation mode can act as a signature for the PPO microenvironment so as to trace the progressive copolymer self-association throughout the irradiation time. In H-1 solid-state NMR, the dependence of the H-1 chemical shift on the PPO hydration state has been exploited to evidence the extent of mesostructuration.