AbstractProtective layers are essential for Si-based photocathodes to achieve long-term stability. The conventionally used inorganic protective layers, such as TiO₂, need to be free of pinholes to isolate Si from corrosive solution, which demands extremely high-quality deposition techniques. On the other hand, organic hydrophobic protective layers suffer from the trade-off between current density and stability. This paper describes the design and fabrication of a discontinuous hybrid organic protective layer with controllable surface wettability. The underlying hydrophobic layer induces the formation of thin gas layers at the discontinuous pores to isolate the electrolyte from Si substrate, while allowing Pt co-catalyst to contact the electrolyte for water splitting. Meanwhile, the surface of this organic layer is modified with hydrophilic hydroxyl groups to facilitate bubble detachment. The optimized photocathode achieves a stable photocurrent of 35 mA/cm² for over 110 h with no trend of decay.