Poly(N-isopropylacrylamide)-block-poly{6-[4-(4-methylphenyl-azo) phenoxyl 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.