In a typical hydrogen-producing photoelectrochemical cell (PEC), water reduction at the cathode (producing hydrogen) is accompanied by water oxidation at the anode (producing oxygen). This anode reaction is, however, not kinetically favourable. Here we investigate the possibility of utilizing solar energy for biomass conversion by performing the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) at the anode of a PEC. HMF is a key intermediate in biomass conversion, and FDCA is an important monomer for the production of numerous polymers. Using 2,2,6,6-tetramethylpiperidine-1-oxyl as a mediator, we obtained a near-quantitative yield and 100% Faradaic efficiency at ambient conditions without the use of precious-metal catalysts. This reaction is also thermodynamically and kinetically more favourable than water oxidation. Our results suggest that solar-driven biomass conversion can be a viable anode reaction that has the potential to increase both the efficiency and the utility of PECs constructed for solar-fuel production.