Novel crystallized rutile TiO2 with microstructures ranging from dendrite-like and leaf-like to flower-like are fabricated through the autoclaving of amorphous tetrabutyl titanate (TBT) which assembles in the cores of electrospun PVDF nanowires. The microstructures and properties of these materials are determined through a combination of XRD, XPS, SEM and EDS/TEM studies. The nucleation of rutile nanocrystallites is accomplished through the formation of F atom-substituted soluble TiO6 complexes with Ti–F bonding. The growth of TiO2 is catalyzed by H2O in the hydrothermal solution. The fabricated TiO2–PVDF membranes undergo efficient photomethanation conversion (about 36-fold higher than commercial P25) even for the first six hours under UV illumination, as well as having high stability. The F atoms from the PVDF and the effect of the TiO2 microstructures play a significant role in the corresponding photomethanation ability which can be elucidated from the photoluminescence (PL) studies.