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Oxidic (photo-)catalysts have the potential to play an important role to efficiently implement sustainable feedstocks and green energy sources into future energy technologies. They may be used not only for solar energy harvesting, but also for hydrogen production or being essential for the fabrication of fine chemicals. Therefore, it is crucial to develop a detailed understanding of how the atomistic environment of the catalyst can be designed in order to promote distinct reaction pathways to influence the final product distribution of chemical reactions. In this perspective article, we survey the surface (photo-)chemistry of methanol on rutile TiO2 surfaces and hybrid catalysts based thereon. Especially the role of the surface bifunctionality by Lewis acidic and basic sites combined with the strong impact of point defects such as reduced titanium sites (mainly Ti3+ interstitials) shall be illuminated. It is shown how the selective activation of either O–H, C–H or C–O bonds in the methanol molecule can be used to tune not only the overall conversion, but to switch between oxidative and reductive routes in favor of either deoxygenation, partial oxidation or C–C coupling reactions. Especially the latter ones are of particular interest to introduce methanol from green sources such as biomass as a sustainable feedstock into already existing petrochemical technologies. [ABSTRACT FROM AUTHOR]