Click chemistry constitutes a class of reactions broadly characterized by efficiency, selectivity, and tolerance to a variety of solvents and functional groups. By far the most widely utilized of these efficient transformation reactions is the Cu^I-catalyzed azide–alkyne cycloaddition. This reaction has been creatively employed to facilitate the preparation of complex macromolecules, such as multiblock copolymers, shell or core cross-linked micelles, and dendrimers. This critical review highlights the application of click chemistry, in particular the Cu^I-catalyzed azide-alkyne cycloaddition, to the synthesis of a wide variety of new materials with possible uses as drug delivery agents, tissue engineering scaffolds, and dispersible nanomaterials (83 references).