Bleached softwood mechanical pulp was treated with sodium borohydride to reduce carbonyl groups and dimethyl sulphate to block phenolic hydroxyl groups. Upon irradiation with near ultra-violet light, new phenolic hydroxyl groups and aromatic carbonyl groups formed. Existing mechanisms for photoyellowing require that either aromatic ketones or phenolic hydroxyls be initially present in the pulp, and cannot explain these observations. We interpret our results in terms of light-induced breakdown of etherified arylglycerol-β-arylether structures in lignin. Degradation occurs via the corresponding ketyl radicals, which cleave rapidly at the β-O-4 bond to give a phenoxy radical and an acetophenone enol. The enol tautomerizes to a ketone, while the phenoxy radical is oxidized to coloured groups. We believe that the ketyl route is the main lignin degradative pathway, and estimate that up to 70% of the colour formed during light-induced yellowing is attributable to this reaction.