AbstractEnantioselective synthesis of chiral heterocyclic derivatives is an important and challenging topic in the field of synthetic chemistry. In this work, the first stereocontrolled dimerization‐type homo‐1,3‐dipolar [3+2] cycloaddition reaction of glycine aldimino esters for creating new heterocycles bearing multiple stereogenic centers has been developed through chiral phosphine ligand‐involved silver catalysis. A variety of chiral imidazolidines could be obtained with high yields and good diastereoselectivities as well as excellent enantioselectivities by employing Xing‐Phos as chiral phosphorus ligand. In addition, the silver/Xing‐Phos‐catalyzed homo‐1,3‐dipolar [3+2] cycloaddition reaction is also a facile and novel protocol for catalytic polymerization of bifunctional glycine aldimino esters to give chiral poly(imidazolidine)s with a very narrow molecular weight distribution.magnified image