Li-ion battery technology is considered as the most efficient solution for the electrochemical energy storage. While standard liquid electrolyte - based configurations provide best performances, solid state electrolytes are developed as a safer alternative. Herein, we discuss a three step synthesis procedure of self-doped solid block copolymer electrolyte, combining a single-ion poly(lithium methacrylate-co-oli-goethylene glycol methacrylate) ion conducting block (P(MALi-co-OEGMA)) and a structuring polystyrene block (PS). The macromolecular design allows the formation of a self-standing film with excellent mechanical properties provided by the PS anchoring nanodomains while attaining attractive ionic conductivities of up to 0.02 mS/cm at room temperature. Moreover, the single-ion configuration based on polyanionic backbone affords high transference numbers, close to unity, and alleviates the power limitation encountered in salt-doped solid polymer electrolyte (SPE). The electrolyte exhibits a wide electrochemical stability window up to 4.5 V vs. Li+/Li and promote the formation of stable interfaces at the electrodes. (C) 2015 Elsevier Ltd. All rights reserved.