Finally, an electrolysis process concomitantly converted the fractionated lignin solution on a carbon-based anode to vanillin and syringaldehyde, which find application in the food, pharma and cosmetics industries. Diluted CO2 is reduced to CO (with a single pass conversion efficiency close to 5% at both 10vol% and 20vol% CO2) with a molecular cobalt(II) porphyrin (CoPL) catalyst immobilised on a multiwall carbon nanotube (MWCNT) cathode. Thus, we demonstrate the complete valorisation of lignocellulose and low concentration CO2, which has been enabled by a precious-metal free fractionation-photocatalysis-electrolysis process.