Green hydrogen from photocatalytic water-splitting and photocatalytic lignocellulosic reforming is a significant proposition for renewable energy storage in global net-zero policies and strategies. Although photocatalytic water-splitting and photocatalytic lignocellulosic reforming have been investigated, their integration is novel. Furthermore, biosynthesis can store the evolved hydrogen and fix the atmospheric carbon dioxide in a biocathode chamber. The biocathode chamber is coupled to the combined photocatalytic water-splitting and lignocellulose oxidation in an anode chamber. This integrated system of anode and biocathode mimics a (bio)electrosynthesis system. A visible solar radiation-driven novel hybrid system comprising photocatalytic water-splitting, ligno-cellulose oxidation, and atmospheric CO2 fixation is, thus, investigated. It must be noted that there is no technology for reducing atmospheric CO2 concentration. Thus, our novel intensified technology enables renewable and sustainable hydrogen economy and direct CO2 capture from air to confront climate change impact. The photocatalytic anode considered is CdS nanocomposites that give a low absorption onset (200 nm), high absorbance range (200–800 nm), and narrow bandgap (1.58– 2.4 V). The biocathode considered is Ralstonia eutropha H16 interfaced with photocatalytic lignocel-lulosic oxidation and a water-splitting anode. The biocathode undergoes autotrophic metabolism fixing atmospheric CO2 and hydrogen to poly(3-hydroxybutyrate) biosynthesis. As the hydrogen evolved can be readily stored, the electron–hole pair can be separated, increasing the hydrogen evolution efficiency. Although there are many experimental studies, this study for the first time sets the maximum theoretical efficiency target from mechanistic deductions of practical insights. Compared to physical/physicochemical absorption with solvent recovery to capture CO2, the photosyn-thetic CO2 capture efficiency is 51%. The maximum solar-to-hydrogen generation efficiency is 33%. Lignocelluloses participate in hydrogen evolution by (1–4)-glycosidic bond decomposition, releasing accessible sugar monomers or monosaccharides forming a Cd–O–R bond with the CdS/CdOx nanocomposite surface used as a photocatalyst/semiconductor, leading to CO in oxidised carbox-ylic acid products. Lignocellulose dosing as an oxidising agent can increase the extent of water-splitting. The mechanistic analyses affirm the criticality of lignocellulose oxidation in photocatalytic hydrogen evolution. The critical conditions for success are increasing the alcohol neutralising agent's strength, increasing the selective (ligno)cellulose dosing, broadening the hybrid nanostruc-ture of the photocatalyst/semiconductor, enhancing the visible-light range absorbance, and increasing the solar energy utilisation efficiency.