The phenomenology of the α relaxation process in an amorphous and crystallized specimen of a side-chain LC polyacrylate, based on the azobenzene mesogenic unit, was investigated by thermal and dynamic-mechanical methods. A frequency and temperature analysis was performed. The relaxation behavior of the amorphous sample was described by the WLF equation. The α process of the semicrystalline sample was structured into two components α′ and α″, both following Arrhenius type activation law. This peculiar behavior has been tentatively related to the multidomain structure of the semicrystalline sample.