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Corncob is one of the main by-products of agricultural biomass in corn-producing area. Here, the valorization of corncob polysaccharide components to produce furfural and glucose was studied. Firstly, corncob was treated by high-pressure CO2-H2O; the in situ formed-carbonic acid catalyzed the selective hydrolysis of hemicellulose component with xylo-oligosaccharide and xylan as the main products. The obtained liquid fraction was further upgraded to furfural with H2SO4 as catalyst. After reaction at 140 °C for 1 h, 7.0 g L−1 of furfural was given. The conversion of C5 sugar and the selectivity of furfural was 56% and 72%, respectively. Then, the cellulose component of the residual solid fraction was depolymerized by oxidation-hydrolysis method. The hydroxymethyl group on the cellulose unit was partially oxidized to carboxyl group, which catalyzed the following hydrolysis of the cellulose component to glucose. 17.2 g of glucose per 100 g oxidized solid fraction was given at 170 °C for 6 h with water as the solvent. Additionally, the oxidation-hydrolysis strategy was also performed for the hydrolysis of the industrial furfural residues. [ABSTRACT FROM AUTHOR]