Exploring reliable electrolytes for aluminum ion batteries requires an in-depth understanding of the behavior of aluminum ions in ethereal-organic solvents. Electrolytes comprised of aluminum trifluoromethanesulfonate (Al-triflate) in tetrahydrofuran (THF) were investigated computationally and experimentally. Optimized geometries, redox potentials, and vibrational frequencies of species likely to be present in the electrolyte were calculated by density functional theory and then measured spectroscopically and electrochemically. Aluminum appears to be electrochemically active in THF with a reduction onset near 0 V versus Al/Al3+. Spectroscopic measurements reveal explicit evidence for the presence of two concentration-dependent ionic environments for the triflate anions, namely, outer-shell ligands and AI-bound triflates. Additionally, ionic conductivities of similar to 2.5 mS/cm were measured for these electrolytes similar to 0.8M.