A highly effective aqueous lubrication strategy employing electrostatic assembly of a negatively charged ultrahigh molecular weight natural polysaccharide named "sacran" and a positively charged poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMTAC) brush was investigated. The PMTAC brush was compressed through the adsorption of sacran to produce the layered structure of a PMTAC brush/sacran hybrid bottom layer and a poorly hydrated sacran top layer. The dynamic friction coefficients of the PMTAC brush were drastically reduced in salt-free sacran aqueous solutions, and the lubrication mode transition from the brush-lubrication regime to hydrodynamic lubrication was promoted. The electrostatic assembly was inhibited by the addition of NaCl into the lubricant solutions, leading to the loss of the lubrication effect. The hydrodynamic lubrication would be encouraged by the local viscosity enhancement at the friction boundary due to the poorly hydrated and highly viscous PMTAC brush/sacran hybrid film produced by the spontaneous electrostatic assembly.