Covalent complexes of peanut protein isolate (PPI) and corn silk polysaccharide (CSP) (PPI-CSP) were prepared using an ultrasonic-assisted moist heat method to improve the functional properties of peanut protein isolate. The properties of the complexes were affected by the level of corn silk polysaccharide. By increasing the polysaccharide addition, the grafting degree first increased, and then tended to be flat (the highest was 38.85%); the foaming, foam stability, and solubility were also significantly improved. In a neutral buffer, the solubility of the sample with a protein/polysaccharide ratio of 2:1 was 73.69%, which was 1.61 times higher than that of PPI. As compared with PPI, the complexes had higher thermal stability and lower surface hydrophobicity. High addition of CSP could made the secondary structure of PPI change from ordered α-helix to disordered β-sheet, β-turn, and random coil structure, and the complex conformation become more flexible and loose. The results of multiple light scattering showed that the composite solution exhibited high stability, which could be beneficial to industrial processing, storage, and transportation. Therefore, the functional properties of peanut protein isolate glycosylation products could be regulated by controlling the amount of polysaccharide added.