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The production of glucuronic acid (GA) directly from actual biomass via chemocatalysis is of great significance to the effective valorisation of biomass for a sustainable future. Herein, we have developed a one-step strategy for the conversion of cellulose in corncob residue into GA with the cooperation of Au/CeO₂ and maleic acid, achieving a 60.3% yield. Experimental and density functional theory (DFT) results show that maleic acid is effective in the fractionation of cellulose from corncob residue and the depolymerisation of cellulose fragments to glucose, on account of the good capacity for proton migration. Au/CeO₂ is responsible for the selective oxidation of glucose to GA, in which the formation of glucaric acid is restrained, due to the weak capacity of Au/CeO₂ on the proton transfer without the occurrence of the ring-opening reaction of glucose. Therefore, the relay catalysis of Au/CeO₂ and maleic acid enables the production of GA via the complex cascade reactions. This work may provide insight regarding the conversion of actual biomass to targeted products.