To characterize the coating structure, diverse methods such as mercury intrusion, nitrogen adsorption and oil absorption methods have been developed and widely employed. These indirect techniques, however, have some limitation to explain the actual coating structure. Recently microscopic observation methods have been tried for analyzing structural characteristics of coating layers. Preparation of the undamaged cross section of a coating layer is essential for obtaining high quality image for analysis. In this study, distortion-free cross-section of the coating layer was prepared using a grinding and polishing technique. The coated paper was embedded in epoxy resin and cured. After curing the resin block it was ground with abrasive papers and then polished with diamond particle suspension and nylon cloth. Polished coating layer was sufficient enough to obtain undamaged cross sectional images with scanning electron microscope under backscattered electron image mode. In addition, the SEM images allowed distinction of the coating layer components. Also S/B latex film formed between pigment particles was visualized by osmium tetroxide staining. Pore size distribution and pore orientation were evaluated by image analysis from SEM cross-sectional images.