Herein, we report the catalytic use of multifunctional CuO nanoparticles (NPs) to oxidatively fractionate lignocellulosic feedstock with dioxygen in aqueous NaOH under mild conditions . In presence of CuO NPs, lignocellulose is fractionated into three parts, overall yielding 90% carbon efficiency. Lignin is converted to up to 45.6 wt% in organic soluble aromatic aldehyde monomers, rich in vanillin and syringaldehyde, the value surpassing the theoretical one based on b-O-4 bond content, indicating significant cleavage of other ether bonds. All hemicellulose is selectively converted into water soluble small (di)acids, mainly to oxalic acid. Up to 81% of cellulose, in contrast, is obtained as a white crystalline residue with high cellulose purity (over 95%), which can readily be transformed into high quality nanocellulose, useful in many applications.