Selectively breaking the C-O bonds within biomass during catalytic fast pyrolysis (CFP) is desired, but extremely challenging. Herein, we develop a series of metal-oxide nanocomposites composed of W, Mo, Zr, Ti, or Al. It is demonstrated that the nanocomposites of WO-TiO-AlO exhibit the highest deoxygenation ability during CFP of lignin, which can compete with the commercial HZSM-5 catalyst. The nanocomposites can selectively cleave the C-O bonds within lignin-derived phenols to form aromatics by direct demethoxylation and subsequent dehydration. Moreover, the nanocomposites can also achieve the selective breaking of the C-O bonds within xylan and cellulose to form furans by dehydration. The Brønsted and Lewis acid sites on the nanocomposites can be responsible for the deoxygenation of lignin and polysaccharides, respectively. This study provides new insights for the rational design of multifunctional catalysts that are capable of simultaneously breaking the C-O bonds within lignin and polysaccharides.