A glycosylated protein/procyanidin complex was prepared by self-assembly of glycosylated whey protein isolate and proanthocyanidins (PCs). The complex was characterized through endogenous fluorescence spectroscopy, polyacrylamide gel electrophoresis, Fourier infrared spectroscopy, oil–water interfacial tension, and transmission electron microscopy. The results showed that the degree of protein aggregation could be regulated by controlling the added amount of procyanidin, and the main interaction force between glycosylated protein and PCs was hydrogen bonding or hydrophobic interaction. The optimal binding ratio of protein:PCs was 1:1 (w/w), and the solution pH was 6.0. The resulting glycosylated protein/PC compounds had a particle size of about 119 nm. They exhibited excellent antioxidant and free radical-scavenging abilities. Moreover, the thermal denaturation temperature rose to 113.33 °C. Confocal laser scanning microscopy (CLSM) images show that the emulsion maintains a thick interface layer and improves oxidation resistance with the addition of PCs, increasing the application potential in the functional food industry.