Electrochemical properties of pulp fiber could be modified by LbL(Layer-by-Layer) multilayering. Salt concentration and pH affect the conformation and ionization degree of polyelectrolyte. In this study, therefore, we intended to evaluate the effect of pH and salt concentration in polyelectrolyte multilayering on the electrochemical properties of pulp fiber. The pH of the stock was varied to 4, 7, and 10. Salt concentration was controlled at 0.001, 0.003, and 0.005 M of NaCl. Higher zeta potential was obtained when pulp fibers were multilayered at the condition of higher pH and higher salt concentration. The final zeta potential of pulp fiber after multilayering was dependent on the adsorption ratio of polyelectrolyte and the initial zeta potential of fibers.