The Cu(I)-catalyzed azide-alkyne click polymerization is well developed and broadly applied to the preparation of functional polymers. The removal of copper residues from the resultant polymers is, however, difficult. One way to completely circumvent this difficulty is to develop click polymerization without the use of metallic catalysts, i.e., metal-free click polymerization (MFCP). Herein, recent efforts towards developing MFCP of activated alkynes and azides, and of activated azides and alkynes, to produce regioregular polytriazoles are summarized, and the properties and applications of the resultant polymers are also briefly discussed.