This study was carried out to improve coating structure by controlling the electrostatic interaction of coating components and by changing the coating structure of coated paper prepared with amphoteric and anionic latices. The results indicated that amphoteric latex copolymerized with carboxylic and amine groups had stronger interaction with other coating components than anionic latex with branched carboxylic group by controlling pH. These properties of amphoteric latex showed positive effects on viscosity rheology, and supernatant sediment of coating color. The coated paper using amphoteric latex had also produced more porous and smoother coverage of the coating layer than that using anionic latex. This porous and smooth coating layer showed better optical properties and printability than those of anionic latex such as opacity, porosity, ink set-off, and wet ink receptivity.