In this paper we report on the synthesis of comb-like copolymers as solid polymer electrolytes (SPE). The synthesis involved anionic polymerization of styrene (St) and 4-vinylanisole (VA) as the followed by grafting of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization (ATRP). The comb-like copolymer's structure was analyzed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The membranes were made by solvent casting and the morphologies were analyzed by atomic forces microscopy (AFM) and scanning electron microscopy (SEM). We observed that a nano and micro phase separation occurs which improves ionic conductivity. The ionic conductivities were determined by AC Impedance, which showed that the SPEs have good conductivities (10−5 Scm−1) at room temperature owing to the negligible values (<10 kJ mol−1) of the activation energies for conductivity. The batteries with these polymers exhibit a capacity of 146 mAh g−1 at C/24, and no evidence of degradation after intense cycling was observed. However, poor cycle life was observed at C/6 and C/3, which is a consequence of several factors. We partially explain that behavior by arguing that whereas PEO lightly “solvates” Li+ thus slowing Li-ion mobility, and PEGMA chains “solvate” Li ions too strongly, trapping and inhibiting their mobility.