The structural and electrochemical properties of various Li–Al–Mn–O–F spinels were studied. Li[Li x Al y Mn2−x−y ]O4−z F z (x =0, 0.05, y =0, 0.1, 0≤ z ≤0.2) spinels were synthesized by a solid-state reaction method. Fluorine substitution in Li[Li x Al y Mn2−x−y ]O4−z F z led to well-developed crystallization with octahedral morphology. In addition, Li[Li x Al y Mn2−x−y ]O4−z F z showed superior cycling performance and better thermal stability than LiMn2O4 and LiAl0.1Mn1.9O4. Fluorine substitution also suppressed Mn dissolution which led to stable cycling performance at 55°C. The differential scanning calorimetry (DSC) results showed that the anion (F for O) and cation (Li, Al for Mn) substituted spinel had better thermal stability than LiMn2O4, Li[Al y Mn2−y ]O4, or Li[Li x Al y Mn2−x−y ]O4.