Mitigation of anthropogenic CO2 accumulation is essential to tackle the current climate change and loss of biodiversity. Large scale global efforts are ongoing to develop CO2 conversion technologies for green fuel production. Solar-driven CO2 conversion is a promising approach to produce clean fuels and chemicals as it directly utilizes sunlight as the sole energy input. However, current CO2 utilization processes depend on pure and pressurized CO2 as reactant, whose production from post-combustion emission streams and air is energy intensive (~2 GJ tonCO2 -1 or 100 kJ molCO2 -1 ). Majority of this energy demand (~80%) is from desorption and compression steps following CO2 capture, involving heating large volumes of alkanolamine solutions and subsequent pressurization of the released gas (Figure ). Direct solar-driven utilization of captured CO2 species is therefore a more attractive way to reach net-zero carbon cycle, but barely explored due to their thermodynamic stability. Thermo-catalytic hydrogenation of captured CO2 has recently been reported at elevated temperatures (100-150 ºC). Electrochemical reduction of alkanolamine captured CO2 can also be achieved over metallic electrodes (Ag, Cu, etc.) at ambient temperatures. Recent studies have shown smallscale localized in situ CO2 gas adsorption followed by photocatalytic conversion in homogeneous and colloidal solutions. Nevertheless, sunlight-driven direct capture and utilization processes with industrially relevant amine/hydroxide capturing agents is lacking, presumably due to the overwhelming energy barrier to activate the trapped CO2-adducts (Figure ). Here we report an integrated CO2 capture and solar-driven photoelectrochemical (PEC) utilization process to produce syngas (mixture of CO and H2), a precursor for industrial liquid fuels and chemicals syntheses, from concentrated CO2 stream, simulated post-combustion flue gas, and atmospheric air. The process operates by combining CO2-to-fuel reduction with selective oxidation of waste plastic-derived ethylene glycol (EG) to glycolic acid (GA), which has applications in pharmaceutical, food and textile industries (Figure ). The system captures CO2 in an aqueous amine or glycolic hydroxide solution and the subsequent PEC conversion occurs in a two-compartment, two-electrode reactor equipped with a triple cation perovskitebased photocathode. Captured CO2 reduction is enabled by an immobilized molecular Cophthalocyanine catalyst at the photocathode. A bimetallic Cu26Pd74 alloy anode completes the circuit by catalyzing EG oxidation. Replacing anodic water oxidation (G 0 (H2O/O2) = +237 kJ mol -1 ) by EG oxidation (G 0 (EG/GA) ~ +20 kJ mol -1 ) makes the demanding captured CO2 reduction feasible with only sunlight, enabling the system to function even with a single visiblelight absorber without any external applied voltage, with simultaneous waste valorization. , where CO2 is first captured from post-combustion gases (step 1), followed by heat treatment to desorb CO2 (step 2). The released CO2 is then compressed and subsequently used for conversion (steps 3 and 4). b, Integrated one-step photoelectrochemical (PEC) approach reported in this study, where the post-capture solution is directly used for conversion using solar energy, to generate syngas as energy vector while at the same time upcycling plastic waste derived ethylene glycol to the commodity chemical glycolic acid. The abbreviations for the individual photocathode layers are in the Method section.