In this study, we modified the surface of ground calcium carbonate (GCC) with polyelectrolytes with different molecular weight using Layer-by-Layer (LbL) multilayering technique and investigated its effect on the paper properties. Polydiallydimethylammonium chloride (poly-DADMAC) and poly sodium 4-styrene sulfonate (PSS) which have different molecular weights were used for LbL multilayering. Zeta potential and particle size of the LbL modified GCC were measured. After preparation of handsheets, their structural and mechanical properties were evaluated. The zeta potential and average particle size of the modified GCC were affected by the molecular weight of anionic polyelectrolyte (PSS). The zeta potential was higher and the particle size was smaller when GCC was treated by PSS with high molecular weight compared to the case with low molecular weight of PSS. The tensile and internal bond strength of the handsheets was increased with an increase in the number of layers on GCC particles, but the molecular weight of polyelectrolyte did not significantly affect the paper strength.