There have been many efforts to enhance the performance and the stability of Li-ion battery. It is crucial to develop a new material as well as to understand the mechanism of microstructure formation of the electrode in order to enhance the performance of the battery. In this study, the effect of sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) on the microstructure formation as well as on the rheological properties in the aqueous anode slurries is investigated. The graphite particles aggregate with each other due to their hydrophobicity and form a gel structure in an aqueous slurry. Both CMC and SBR induce the dispersion of the graphite particles by adsorbing onto the graphite surface. In the graphite/CMC/SBR slurry, the SBR can affect the dispersion of the graphite particles at low CMC concentration, while the microstructure is not changed regardless of added SBR at high CMC concentration because the SBR cannot adsorb on the graphite surface due to the presence of CMC. The microstructure of the slurry is also confirmed by the cryo-SEM images. Understanding the role of the binders on the microstructure formation will be helpful for the effective design of the battery slurries.