Cu(i)-catalyzed azide–alkyne click polymerization has been widely applied in diverse areas. However, the removal of metal residues from the products is not a trivial task. To completely surmount this difficulty, the metal-free click polymerization (MFCP) of azides and alkynes is highly demanded. In this chapter, the recent developments of alkyne–azide MFCP are summarized, and the properties and applications of the resultant polytriazoles are introduced. Meanwhile, the opportunities and challenges in this area are also briefly discussed.