A new method of preparing a cassava starch-based wood adhesive with high performance using hydrogen peroxide, acrylamide, butyl acrylate (BA), and an organic siloxane as an oxidant, a hard co-monomer, a soft co-monomer, and crosslinking agent, respectively, is proposed. The effects of various parameters on the shear strength, the water resistance, and the viscosity of the adhesive were investigated. The results showed that the shear adhesive strength in dry state and wet state of cassava starch-based adhesive could reach 6.11 MPa and 3.05 MPa, respectively. The organic siloxane, when added, could reduce the content of the hydroxyl on the starch molecule, and promote the crosslinking of the starch molecules, improving the bonding strength and water resistance.