For two-electrode PEC captured CO2 conversion coupled to EG oxidation, the catholytes were captured CO2 solution with additives (similar to Figure ) and the anolytes were 0.5 M EG in 0.5 M aqueous KOH (TEA/H2O) or 0.6 M NaOH, 0.15 M TBABF4 in 80/20 EG/MeCN solution (NaOH/EG). The two compartments were separated by a bipolar membrane to maintain the pH difference which introduced a chemical bias (~0.35 V) to the system. CV scans under solar-irradiation showed an onset voltage at -0.4 V for the TEA/H2O system with j ~4.9 mA cm -2 at zero applied voltage (Figure ). A stable photocurrent density of 1.1±0.3 mA cm -2 was obtained during PEC experiment without any external voltage under chopped light irradiation (1 sun, 50 min on, 10 min off, Figure ). After 10 h, syngas was detected in the cathode with 54.6±9.2 mol cm -2 CO and 106.6±8.4 mol cm -2 H2 (FECO 34.1±2.2% and FEH2 70.3±1.8%, Figure ). The turnover number of the molecular catalyst for CO formation (TONCO) was estimated 3657±591 (Figure ). No other reduction products were detected in NMR spectroscopic analysis of the catholyte. The high performance liquid chromatography (HPLC) analysis of the anolyte showed GA as only oxidation product with 85.8±16.2 mol cm -2 yield (FEGA 92.5±5.3%). The possibility of employing real-world PET waste as EG precursor was confirmed by using alkaline pre-treated commercial PET plastic bottle solution as anolyte (~0.2 M EG, see methods), which showed similar yields and FE for H2, CO, and GA formation after 10 h of PEC experiment without external voltage (Figure ).