The coating structure is directly related to quality of coated paper, especially printability. Its structure mainly consists of pigment, binder, and additives. Binder has a significant influence on the coating structure because it is involved in the structure forming process and takes a key role in maintaining the structure. In this study, styrene acrylate (S/A) latex with hydroxyethyl methacrylate (HEMA) as a comonomer was used as a binder, and the influence of HEMA contents on latex swelling and coating structure was investigated. The S/A latex particle swelled more with an increasing HEMA content, which significantly influenced coating color and coating layer characteristics. The viscosity of coating color became thick, and the dewatering of coating color was suppressed. The HEMA monomer that swelled latex particle allowed the coating layer to consolidate rapidly, which made the coating layer more porous and more uniform.