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Solid Li-Ion Conductors (SLICs) containing more than one Li-ion per repeat unit are prepared by bis-chlorosulfonation of poly(ether ether ketone) followed by reaction with commercially available amines and sulfonamides pre-treated with n -BuLi, including 3-trifluoromethyl aniline, 3-(lithium sulfonate aniline), methanesulfonamide, trifluoromethylsulfonamide, 6-picolinylsulfonamide and p -tolylsulfonamide. These SLICs contain two sulfonamide or bis-sulfonimide groups and in some cases, additional sulfonate groups. Up to 4 Li ions can be introduced in the repeat unit by this procedure. The characterization includes NMR, FTIR and electrochemical impedance spectroscopy. The ionic conductivity of these new SLiCs is significantly higher than the reference polymers with only Li-ion per repeat unit and reaches more than 10−4 S/cm for some bis(sufonylimide) derivatives. The cycling efficiency of a Li-metal battery with TiO 2 nanotubes as positive electrode and a separator film from a SLIC with 4 Li-ions per repeat unit is quite high up to 3C discharge rate. The Coulombic efficiency is near 100 % after the first cycle. • Synthesis of solid polymer electrolytes with several Li-ions per repeat unit. • Single Li-ion conductivity exceeds 0.1 mS/cm at room temperature. • Li-metal battery shows good cycling capacity up to 3C rate. [ABSTRACT FROM AUTHOR]