The microstructure of coating layers has important effects on final properties of paper. Eco-friendly bio-latex derived from sustainable starch has being increasingly used in paper coatings to substitute part of the petroleum-based synthetic latex as pigment binder. The influence of starch-based bio-latex on microstructure and surface properties of coatings such as surface composition, surface morphology, void fraction and water absorbency was studied in this paper. X-ray photoelectron spectroscopy (XPS) results showed that bio-latex addition led to a nearly linear decrease in surface carbon content for coatings dried at high temperature. Scanning electron microscope (SEM) images demonstrated that bio-latex addition may cause a lack of binder film at the coating surface that binds pigment particles, which was in agreement with the XPS results. The coatings demonstrated a marginal increase in surface roughness and some decrease in gloss with the addition of bio-latex, as was expected when starch-based binder was used. Unexpectedly, the void fraction of coatings increased slightly, which was contrary to the case in conventional cooked starch. The coatings had a significant decline in water contact angle after bio-latex addition, indicating a considerable increase in water absorbency. The changes in coating microstructure may be attributed to the unique core-shell structure and water-swollen nature of starch-based bio-latex particles.