The two-electrode two-compartment PEC experiments were carried out with PVK|CoPcNH2@MWCNT photocathode and Ni foam|Cu26Pd74 as the dark anode, where captured CO2 conversion to syngas and EG oxidation to GA were performed simultaneously under 1 sun solar irradiation without applying any external voltage. The catholytes were capture solution + 0.1 M K2SO4 (aqueous medium) or capture solution + 20% v/v MeCN + 0.15 M TBABF4 (organic medium), and the anolytes were 0.5 M KOH, 0.5 EG in water (aqueous medium) or 0.6 M NaOH, 0.15 M TBABF4 in 80/20 v/v EG/MeCN solvent mixture (organic medium). CV scans in this two-electrode configuration were recorded at 10 mV s -1 scan rate to observe the photoelectrochemical response under chopped, continuous, and no light irradiation. The PEC experiments were carried out under chopped irradiation (50 min on, 10 min off) at no applied voltage for a certain time period, and the obtained photocurrents were normalized to the perovskite active area. Product analysis and quantification was carried out after each PEC experiment.