Collagen extracted from leather waste was modified with maleic anhydride. Then, using ammonium persulfate as an initiator, by pre-modifying collagen reacted with styrene and ethyl acrylate monomers, a vinyl-grafted collagen sizing agent (VGCSA) for paper was prepared. Before the experiment, the performance of VGCSA was tested and VGCSA emulsion was applied to the surface sizing of the corrugated paper. Effects of the amount of VGCSA, the compound proportion of VGCSA, and starch and styrene-acrylic emulsion were studied relative to paper properties. The morphological changes of the paper before and after sizing were characterized by SEM. It was found that the collagen reacted with styrene and ethyl acrylate monomers. Through the grafting of vinyl and collagen, the crystallinity and thermal stability of VGCSA increased. The structure of VGCSA was spherical with a uniform size, and the average particle size was approximately 350 to 400 nm. After being sized, the surface fibers of paper became smooth and orderly. The optimal sizing of VGCSA was 8 g/m2. The optimal proportion of VGCSA with starch was 4:6, and the optimal proportion of VGCSA with SAE was 2:8. The research indicates that collagen extracted from leather waste could be used as a biomaterial, and environmental and economic benefits could be created as well.