AbstractDynamic mechanical properties of substituted polypentenamers having thioglycolate side groups and their hydrogenated derivatives have been studied. Methyl esters, acids and salts were investigated at two concentrations, 5.5 mole (%) and 9.2 mole (%). In the un‐hydrogenated derivatives one principal relaxation, labelled β, exists in the temperature range from‐160 to 100°C. This relaxation arises from microbrownian segmental motion accompanying the glass transition. Its temperature is affected by the concentration of substituent but not the chemical nature of the substituent. A ‘rubbery plateau’ region exists in the acid and salt derivatives and in the latter the salt groups act as reinforcing fillers in this plateau region, consistent with the ionic domain model for their structures.In the hydrogenated derivatives, three relaxations occur in the temperature range from −160 to 120°C and these are labelled α, β, and γ in order of decreasing temperature. The α relaxation arises from motions associated with the crystal phase except in the case of the 9.2 mole (%) sodium salt derivatives where it arises from motions occurring within ionic domains. The β relaxation arises from microbrownian segmental motions accompanying the glass transition, and the γ relaxation arises from localised motions which may involve both amorphous and crystallin