AbstractTransesterifications ofatacticandisotacticpoly(methyl acrylate) with optically active alcohols such as (S)‐2‐methyl‐butanol, D‐borneol and L‐menthol were carried out in toluene at 100°C usingp‐toluenesulfonic acid as catalyst to obtain optically active polymers. In addition a relationship between the conformation and the optical behaviour of the transesterified poly(methyl acrylate) was investigated. The specific rotation of the transesterifiedatacticpoly(methyl acrylate) increased linearly with increasing introduced optically active groups at the lateral chain, in contrast to that of theisotacticpoly(methyl acrylate) which increased nonlinearly with increasing introduced asymmetric groups. Since the specific rotations of the transesterified polymers depend on these tacticities the conclusion was drawn that the optical activity is caused not only by the asymmetric group in the lateral chain but also by molecular dissymmetry in the pri