The pore structure of the coating layer is one of the most important factors in determining the printability of coated papers. The coating pigment and binder are two principal components in paper coating, and their characteristics have a critical influence on the coating structure. The glass transition temperature (Tg) of latex binders affects the mechanical strength and pore structure of the pigment coating layer because the latex Tg influences the binding ability of latex and the shrinkage of the coating layer during the drying process. In this study, styrene-acrylate (S/A) core-shell structure latexes with different monomer compositions in the core and shell layers were designed, and their properties were compared with those of a conventional latex. These core-shell latexes were prepared using the same monomers in the same proportion and were used to investigate the effect of the core-shell structure on the structural and mechanical properties of the coating layer. The hard-shell latex with a high styrene content in the shell part yielded paper that was glossier and less rough and formed finer pores, resulting in an increased ink absorption rate into the coated paper compared to the other types of latex. The hard-shell structure showed better performance in printing uniformity and had less mottling.