Herein, a convenient and general method to simultaneously fix and functionalize polymeric vesicles with sulphydryl groups by the co-self-assembly of poly(ethylene oxide)-block-poly[3-(triethoxysilyl)propyl methacrylate] (PEO-b-PTESPMA) and 3-mercaptopropyltrialkoxysilane in an aqueous solution is reported. The presence of sulphydryl groups across the vesicle membrane has been confirmed by using an energy-filtered technique during TEM analysis and by capturing Au nanoparticles.