AbstractUnder microwave irradiation and solvent‐free conditions, rare‐earth metal chlorides (RECl3) have been efficient catalysts for one‐pot synthesis of quinoline derivatives to give products in good to excellent yields through the multi‐component reactions of aldehydes, amines, and alkynes. The rare‐earth metal chlorides can be recycled for six times without notable loss of catalytic activities. This new synthetic approach has prominent features of a short reaction time, high yields of products, operational simplicity, broad substrate scopes, environmentally friendly property and commercially available catalysts. It extends the applications of rare‐earth metal compounds as catalysts in organic synthesis.