Syndiospecific polymerization is a stereospecific chain-growth process in which successive monomer insertions generate predominantly syndiotactic dyads and triads, that is, an alternating relative configuration of adjacent stereocenters along the polymer backbone. The defining stereochemical outcome is a high racemo (r) dyad content and corresponding rrr triad enrichment, as opposed to the meso (m) enrichment that characterizes isospecific polymerization. In coordination mechanisms, facial selection at the metal active site and chain-end control cooperate to dictate the sense of each insertion so that opposite absolute configurations alternate ^[1]. Homogeneous titanium-based catalysts activated by methylaluminoxane exemplify systems that polymerize styrene by repeated insertion to give crystalline syndiotactic polystyrene ^[1]. Quantitative NMR triad analysis and first-order Markov statistics are used to demonstrate that the steric control is syndiotactic-specific rather than atactic or isotactic ^[2]. The concept is thereby bounded as stereoregulating polymerization that produces syndiotactic sequences, distinct from nonstereospecific radical or ionic polymerizations that yield atactic chains.