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Interfacial properties currently hinder the performance of Si/organic heterojunction solar cells for an alternative to high-efficiency and lowcost photovoltaics.Here, we present a simple and repeatable wet oxidation method for developing the surface passivation layer, SiOx, on the Si surface for the fabrication of high-efficiency Si/poly(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS)heterojunction solar cells.The uniform and dense SiOx thin layer introduced by the oxidizing aqueous solution of H2O2 or HNO3 provided the better surface passivation and stronger wettability of the Si surface, compared to those in the native oxide case.These two types of progress helped create a lower defect density at the Si/PEDOT:PSS interface and thus a high-quality p-n junction with a lower interface recombination velocity.As a result, the HNO3-oxidized device displayed better performance with a power conversion efficiency (PCE) of 11%, representing a 28.96% enhancement from the PCE of 8.53% in the native oxide case.The effects on the performance of the Si/PEDOT:PSS hybrid solar cells of the wet oxidation treatment procedure, including the differences in surface roughness and wettability of the Si substrate, the quality and thickness of the SiOx, etc., were explored extensively.Such a simple and controllable oxidizing treatment could be an effective way to promote the interfacial properties that are an important cornerstone for more efficient Si/organic hybrid solar cells.