High-optical-quality titania-based mesostructured films with cubic or 2D-hexagonal symmetry were fabricated by combining trifluoroacetate (TFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide) -poly(ethylene oxide) (PEO-PPO-PEO) copolymers. The distribution, dynamics, and local environments of the TFA-modified titania, PEO, and PPO components of the hybrid were investigated. IR/Raman spectroscopy, in situ small-angle X-ray scattering, and transmission electron microscopy studies indicate that TFA coordinates the titanium center and forms a stable complex that is subsequently organized by the block copolymer species into ordered mesostructures. Solid-state NMR F-19 ->H-1 cross-polarization, C-13{H-1} two-dimensional heteronuclear correlation, and H-1 relaxation techniques were used to determine that PEO is predominantly incorporated within the TFA-modified titania, and that PPO environments encompass both microphase separated regions and interfacial regions composed of mixed PPO and TFA-modified titania. NMR F-19 multiple-quantum spin counting measurements suggest that -CF3 groups of the trifluoroacetate ligands do not form clusters but instead randomly distribute within the inorganic component of the hybrid.