The development of fundamental synthetic chemistry of acetylenic polymers, which not only refers to polyacetylenes but also to all the polymers synthesized from acetylenic monomers containing single or multiple carbon–carbon triple bonds, is summarized in this review. The design of new monomers with one, two, and three triple bonds, explorations of functional tolerant organic and organometallic catalysts, and development of effective linear and nonlinear triple bond‐based polymerization processes have led to successful syntheses of a large variety of acetylenic polymers with miscellaneous structures and advanced specialty properties.