Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource‐efficient synthesis of inorganic materials. This Review covers chemical reactions of various deep eutectic solvents and types of ionic liquids, including metal‐containing ionic liquids, [BF₄]⁻‐ or [PF₆]⁻‐based ionic liquids, basic ionic liquids, and chalcogen‐containing ionic liquids. Cases in which cations, anions, or both are incorporated into the final products are also included. The purpose of this Review is to raise caution about the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.

The alkylation of isobutane with butene is an important refining process for the production of a complex mixture of branched alkanes, which is an ideal blending component for gasoline. The current catalysts used in industrial processes are concentrated H₂SO₄ and HF, which have problems including serious environmental pollution, equipment corrosion, potential safety hazard, high energy consumption in waste acid recycling, etc. Solid catalysts are another type of catalyst for this alkylation; however, they suffer from problems related to rapid deactivation. Ionic liquids (ILs) can be considered as catalysts of the third generation to replace traditional catalysts in isobutane/butene alkylation to produce clean oil. In this review, alkylation catalyzed by various kinds of acidic ILs, including Lewis acidic ILs (such as chloroaluminate ones) and ILs containing Brønsted acidic functional groups (e.g., –SO₃H, [HSO₄]⁻), is reviewed. The currently reported ILs used in the catalysis of isobutane alkylation and their corresponding catalytic activity are summarized and compared. This will help the readers to know what kinds of ILs are effective for the alkylation of isobutane with butene and to understand which factors affect the catalytic performance. The advantages of the catalysis of isobutane/butene alkylation by ILs include tunable acidity of the catalyst by varying the ion structure, limited solubility of the products in the IL phase and therefore easy separation of the alkylate from the catalyst, environmental friendliness, less corrosion of equipment, etc., thus making catalysis by ILs greener. The mechanism and kinetics of the alkylation catalyzed by ILs are discussed. Finally, perspectives and challenges of the isobutane/butene alkylation catalyzed by ILs are given.