Disubstituted acetylene monomers [1,2‐diphenylacetylenes (DPAs: DPA‐pC1, DPA‐mC1, DPA‐pC8); 1‐phenyl‐2‐hexylacetylene (PHA‐pC1)] are tested for asymmetric polymerization in chiral monoterpenes used as solvents and compared with the corresponding monosubstituted acetylene monomer [1‐phenylacetylene (PA‐pC1)]. DPA‐pC1 containing a trimethylsilyl group in the para‐position of the phenyl ring produces an optically active polymer with a large Cotton effect, despite the absence of a stereogenic center. The polymer sample obtained by polymerization in 87% ee (–)‐α‐pinene shows the strongest CD signal (gCD value at 385 nm: ∼3.2 × 10−3). The Cotton bands of the polymers obtained in (–)‐ and (+)‐α‐pinenes show the opposite sign in the CD signals. Theoretical calculations show that only the cis‐cisoid model adopts a helical conformation. A time‐correlated single photon counting experiment shows that the emission of the chiral polymer originates from a virtually single excited species with a 98% component fraction. This polymer solution does not show any significant decrease in gCD value over a wide temperature range of 20 to 80 °C. No noticeable decrease in the gCD value is detected when the polymer solution is kept at relatively low temperatures for a prolonged period (35 d). In contrast, the other polymers show no CD signal.
