The surface functionalization of TiO2-based materials with alkylsilanes is attractive in several cutting-edge applications, such as photovoltaics, sensors, and nanocarriers for the controlled release of bioactive molecules. (3-Aminopropyl)triethoxysilane (APTES) is able to self-assemble to form monolayers on TiO2 surfaces, but its adsorption geometry and solar-induced photodegradation pathways are not well understood. We here employ advanced experimental (XPS, NEXAFS, AFM, HR-TEM, and FT-IR) and theoretical (plane-wave DFT) tools to investigate the preferential interaction mode of APTES on anatase TiO2. We demonstrate that monomeric APTES chemisorption should proceed through covalent Si-O-Ti bonds. Although dimerization of the silane through Si-O-Si bonds is possible, further polymerization on the surface is scarcely probable. Terminal amino groups are expected to be partially involved in strong charge-assisted hydrogen bonds with surface hydroxyl groups of TiO2, resulting in a reduced propensity to react with other species. Solar-induced mineralization proceeds through preferential cleavage of the alkyl groups, leading to the rapid loss of the terminal NH2 moieties, whereas the Si-bearing head of APTES undergoes slower oxidation and remains bound to the surface. The suitability of employing the silane as a linker with other chemical species is discussed in the context of controlled degradation of APTES monolayers for drug release and surface patterning.