Poly(N‐isopropylacrylamide)‐block‐poly{6‐4‐(4‐methylphenyl‐azo) phenoxy] hexylacrylate} (PNIPAM‐b‐PAzoM) was synthesized by successive reversible addition‐fragmentation chain transfer (RAFT) polymerization. In H2O/THF mixture, amphiphilic PNIPAM‐b‐PAzoM self‐assembles into giant micro‐vesicles. Upon irradiation of light at 365 nm, fusion of the vesicles was observed directly under an optical microscope. The real‐time fusion process is presented and the derivation is preliminarily due to the perturbation by the photoinduced trans‐to‐cis isomerization of azobenzene units in the vesicles.
