Living/controlled polymerization techniques have enabled the synthesis of a large variety of different well-defined (co)polymer structures. In addition, the use of click chemistry in polymer science is a quickly emerging field of research since it allows the fast and simple creation of well-defined and complex polymeric structures in yields that were previously unattainable. In this critical review, the application of the azide–alkyne 1,3-dipolar cycloaddition for the construction of well-defined polymer architectures will be discussed in detail, providing a comprehensive overview for all disciplines related to polymeric materials.