It is possible to prepare elastic and thermoreversible gel electrolytes with significant electroactivity by dissolving minimal weight fractions of Ultra High Molecular Weight poly(ethylene oxide) (UHMW PEO) in an aluminum deep eutectic solvent (DES) electrolyte composed of AlCl 3 and urea at a molar ratio of 1.5:1 (AlCl 3 :urea). The experimental vibrational spectra (FT-IR and Raman) provide valuable information on the structure and composition of the gel electrolyte. However, the complexity of this system requires computational simulations to help interpretation of the experimental results. This combined approach allows us to elucidate the speciation of the DES liquid electrolyte in the gel and how it interacts with the polymer chains to give rise to an elastic network that retains the electroactivity of the liquid electrolyte to a very great extent. The observed reactions occur between the ether in the polymer and both the amine groups in urea and the aluminum species. Thus, similar elastomeric gels may likely be prepared with other aluminum liquid electrolytes, making this procedure an effective way to produce families of gel aluminum electrolytes with tunable rheology and electroactivity.