The sol–gel technique followed by conventional (TiO2-1) and hydrothermal (TiO2-2) thermal treatment was employed to prepare TiO2-based photocatalysts with distinct particle sizes and crystalline structures. The as prepared metal oxides were evaluated as photocatalysts for gaseous HCHO degradation, methanol, and dye oxidation reactions. Additionally, metallic platinum was deposited on the TiO2 surfaces and H2 evolution measurements were performed. The photocatalytic activities were rationalized in terms of morphologic parameters along with the electron/hole dynamics obtained from transient absorption spectroscopy (TAS). TiO2-2 exhibits smaller particle size, poorer crystallinity, and higher surface area than TiO2-1. Moreover the hydrothermal treatment leads to formation of the metastable brookite phase, while TiO2-1 exhibits only the anatase phase. TAS measurements show that the electron/hole recombination of TiO2-2 is faster than that of the latter. Despite that, TiO2-2 exhibits higher photonic efficiencies for photocatalytic oxidation reactions, which is attributed to its larger surface area that compensates for the decrease of the surface charge carrier concentration. For H2 evolution, it was found that the surface area has only a minor effect and the photocatalyst performance is controlled by the efficiency of the electron transfer to the platinum islands. This process is facilitated by the higher crystallinity of TiO2-1, which exhibits higher photonic efficiency for H2 evolution than that observed for TiO2-2. The results found here provide new insights into the correlations between thermal treatment conditions and photocatalytic activity and will be useful for the design of high performance photocatalysts.