In this study, ground calcium carbonate (GCC) was modified by Layer-by-Layer (LbL) multilayering with polyelectrolytes. Cationic polyacrylamide (C-PAM) and poly sodium 4-styrene sulfonate (PSS) were used as cationic and anionic polyelectrolytes to modify GCC. The characteristics of the modified GCC were examined in terms of zeta potential and particle size with the addition level of polyelectrolyte and layer number. The GCC could form an assembly of cationic and anionic polyelectrolytes through consecutive adsorption process. The zeta potential of the modified GCC moved toward the cationicity and reached the plateau with the increase of the addition level of C-PAM. With layering of anionic PSS, the GCC had the negative charge. The particle size was dependent on the zeta potential. It was also observed by optical microscope. As the PSS was in the presence of the outermost layer, the GCC showed the better dispersability. It indicated that the surface charge and particle size can be controlled by adjusting the addition level of polyelectrolyte and the layer number.