Abstract The use of a photoelectrochemical device is an efficient method of converting solar energy into hydrogen fuel via water splitting reactions. One of the best photoelectrode materials is Si, which absorbs a broad wavelength range of incident light and produces a high photocurrent level (~44 mA·cm−2). However, the maximum photovoltage that can be generated in single-junction Si devices (~0.75 V) is much lower than the voltage required for a water splitting reaction (>1.6 V). In addition, the Si surface is electrochemically oxidized or reduced when it comes into direct contact with the aqueous electrolyte. Here, we propose the hybridization of the photoelectrochemical device with a thermoelectric device, where the Seebeck voltage generated by the thermal energy triggers the self-biased water splitting reaction without compromising the photocurrent level at 42 mA cm−2. In this hybrid device p-Si, where the surface is protected by HfOx/SiOx bilayers, is used as a photocathode. The HfOx exhibits high corrosion resistance and protection ability, thereby ensuring stability. On applying the Seebeck voltage, the tunneling barrier of HfOx is placed at a negligible energy level in the electron transfer from Si to the electrolyte, showing charge transfer kinetics independent of the HfOx thickness. These findings serve as a proof-of-concept of the stable and high-efficiency production of hydrogen fuel by the photoelectrochemical-thermoelectric hybrid devices.