Composition of polyacene (PAS)-based negative electrode has been optimized to be suitable for rechargeable battery systems with polymeric gel electrolytes. The gel electrolytes consisted of poly(vinylidenefluoride-co-hexafluoropropylrne) (PVdF-HFP) as a host polymer, a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) as a plasticizer, and LiX (X=ClO4 or (C2F5SO2)2N) as a carrier salt. Three types of composite PAS electrodes were prepared and their compatibility with the polymeric gel electrolytes was examined. A half cell assembled with the composite PAS electrode containing proper amounts of polymeric gel and the electrolyte film with the same gel composition showed good cycling characteristics. The gel composition containing 1.0moldm−3 (M) Li(C2F5SO2)2N/(EC+DEC) gave discharge capacity of about 600Ahkg−1 (with respect to the mass of PAS) with high rechargeability.