Photocatalysis provides an eco-friendly route for the hydrogenation of aromatic carbonyls to O-free aromatics, which is an important refining process in the chemical industry that is generally carried out under high pressure of hydrogen at elevated temperatures. However, aromatic carbonyls are often only partially hydrogenated to alcohols, which readily desorbs and are hardly further deoxygenated under ambient conditions. Here, we show that by constructing an oxide surface over the Pd cocatalyst supported on graphitic carbon nitride, an alternative hydrogenation path of aromatic carbonyls becomes available via a step-wise acetalization and hydrogenation, thus allowing efficient and selective production of O-free aromatics. The PdO surface allows for optimum adsorption of reactants and intermediates and rapid abstraction of hydrogen from the alcohol donor, favoring fast acetalization of the carbonyls and their consecutive hydrogenation to O-free hydrocarbons. The photocatalytic hydrogenation of benzaldehyde into toluene shows a high selectivity of >90% and a quantum efficiency of ∼10.2% under 410 nm irradiation. By adding trace amounts of HCl to the reaction solution, the PdO surface remains stable and active for long-term operation at high concentrations, offering perspective for practical applications.