The asymmetric Friedel–Crafts (AFC) alkylation reaction is one of the most important approaches to the synthesis of optically pure organic compounds. Various catalytic systems, including well-defined organometallic complexes (Zn, Cu, Sc, etc.) and small organic molecules (chiral imidazolidinones, thioureas, prolinols, BINOL-derived phosphoric acids, etc.), have been successfully developed and applied in asymmetric Friedel–Crafts alkylation reactions. Remarkable levels of enantioselectivity have been achieved for electron-rich arenes such as indoles, pyrroles, and naphthols, and electrophiles such as carbonyl compounds, imines, α,β-unsaturated carbonyl compounds, and π-allyl metal species.