Cross-linked polyethylene (CLPE) has been used in artificial joints for more than two decades, and the low wear resistance compared with metal pairs made it produce abrasive debris and led to osteolysis problems with the service period extended. Therefore, the purpose of this study was to graft the zwitterionic monomer [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (MEDSAH), the cationic monomer methacryloyloxyethyl trimethyl ammonium chloride (MTAC) and the anionic monomer sodium styrene sulfonate (NaSS) with good hydrophilicity onto the CLPE surface by UV irradiation to achieve the low friction coefficient and wear rate. FTIR-ATR and XPS spectra showed that all three monomers were successfully grafted onto the sample surface, and the grafting quantity increased with the monomer concentration increasing. Contact angle tests showed that the PMEDSAH, PMTAC, and PNaSS all expressed excellent hydrophilicity (down to 21º, 7.5º, and 14.5º, respectively). Biotribological properties of modified CLPEs in 25% neonatal bovine serum (NBCS) and SBF solutions were investigated, and the results showed that the friction coefficient of the samples decreased significantly with the monomer concentration increasing, and the minimum friction coefficient was obtained at the maximum monomer concentration. After the long-term wear test, the wear rates of the modified samples were all lower than untreated samples. These results confirmed that CLPE surfaces grafted by PMEDSAH, PMTAC, and PNaSS could improve the biotribological properties and revealed the lubrication mechanism of polyelectrolytes under different lubrication.