The search for solid electrolytes for electrochemical devices is an object of intense research due to their benefits compared to the liquids, mainly due to the processability aspects, handling, and leak elimination. Although studies involving solid polymeric electrolytes have been reported, the research for materials that combine good mechanical strength, elasticity, chemical, thermal stabilities, and ionic conductivity is still emerging. In this sense, in this study, we show a facile method to fabricate free-standing solid polymer electrolytes using a block copolymer named poly (ether-block-amide) (PEBA) 2533, ionic liquids (IL), and lithium salt bis(trifluoromethylsulfonyl) imide (LiTf2N). These membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analyses (DMA), Fourier transform infrared spectroscopy (FTIR), and complex impedance spectroscopy. Subtle changes in crystallinity, melting temperature (Tm), glass transition temperature (Tg), and thermal stability have been observed when IL and lithium were incorporated in the neat polymer PEBA. Furthermore, the addition of the different ILs in PEBA afforded membranes with conductivity in the order of 10−6–10−5 S cm−1 at 25 °C and the sample containing EMImTf2N showed Li+ transport number of 0.40, which are satisfactory values for solid electrolytes based on elastomers. This is the first report on the preparation of a solid electrolyte based on PEBA for lithium-ion batteries.