Degradation of the peanut cell wall is a critical step in the aqueous enzymatic extraction process to extract proteins and oil bodies. Viscozyme® L, a compound cell wall degrading enzyme, has been applied as an alternative to protease in the process of aqueous enzymatic extraction, but the mechanism of cell wall enzymolysis remains unclear. The present study aims to investigate the changes in cellulose, hemicellulose, and pectin content of the peanut cell wall hydrolyzed by Viscozyme® L. The degree to which the main components of the peanut cell wall, such as trans-1, 2-cyclohexanediamine-N,N,N’,N’-acetic acid-soluble pectin (CDTA-soluble pectin), Na2CO3-soluble pectin, cellulose, and hemicellulose, are degraded is closely related to the extraction of oil bodies and peanut protein at different solid-liquid ratio of powered peanut seed in distilled water, enzyme concentration, enzyme hydrolysis temperature, and enzyme hydrolysis time. The key sites of Viscozyme® L activity on cell wall polysaccharides were explored by comparing the changes in chemical bonds under different extraction conditions using Fourier-transform infrared spectroscopy (FT-IR) absorption bands and principal component analysis (PCA). Viscozyme® L acted on the C-O stretching, C-C stretching, and CH2 symmetrical bending of cellulose, the C-O stretching and O-C-O asymmetrical bending of hemicellulose, and the C-O stretching and C-C stretching of pectin.