Ab iohybrid photobioanode mimicking the Zscheme has been developed by functional integration of photosystem II (PSII) and PbS quantum dots (QDs) within an inverse opal TiO 2 architecture giving rise to ar ather negative water oxidation potential of about À0.55 Vv s. Ag/ AgCl, 1m KCl at neutral pH. The electrical linkage between both light-sensitive entities has been established through an Oscomplex-modified redox polymer (P Os ), whicha llows the formation of amulti-step electron-transfer chain under illumination starting with the photo-activated water oxidation at PSII followed by an electron transfer from PSII through P Os to the photo-excited QDs and finally to the TiO 2 electrode.T he photobioanode was coupled to an ovel, transparent, inverseopal ATOc athode modified with an O 2 -reducing bilirubin oxidase for the construction of aH 2 O/O 2 photobioelectrochemical cell reaching ahigh open-circuit voltage of about 1V under illumination.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.