In this study, we modified the surface of nanofibrillated cellulose (NFC) through LbL (Layer-by-Layer) multilayering process with polyelectrolytes and investigated the effects of the NFC modification on the charge of NFC surface and the dewatering ability of NFC suspension. The multilayering process was done onto NFC fibers using polydiallyldimethylammonium chloride (PDADMAC) and poly-sodium 4-styrene sulfonate (PSS) under different dosage and washing conditions. When the washing was carried out in every adsorption stage, the modified NFC had strong cationic or anionic charge depending on the type of polyelectrolyte in the outermost layer and the dewatering ability was not affected. In the case of no washing treatment or washing in the final adsorption stage, however, the zeta potential of NFC was close to an isoelectric point so that the dewatering ability increased remarkably. Low addition level of polyelectrolytes also showed the similar results. The mixing of NFC suspensions with opposite charge resulted in higher network strength and improved dewatering ability due to the flocculation.