Abstract: | Well‐defined cyclic‐polymers (cyclic‐PAzoMMAs), bearing side‐chain phenylazo naphthalene chromophore, were successfully synthesized by the combination of atom transfer radical polymerization (ATRP) and copper(I)‐catalyzed azide/alkyne cycloaddition “click” reaction, as verified by GPC, 1H NMR, FTIR, and MALDI‐TOF mass spectrometry. The cyclic‐PAzoMMA showed higher glass transition temperatures than the linear‐PAzoMMA with the same molecular weight. Interestingly, the cyclic‐PAzoMMA exhibited deeper modulation depth (M.D.) induced by SRG, larger value of the photoinduced birefringence, increased fluorescence emission, and longer fluorescence lifetime in comparison with its linear counterpart. |