A novel system was reported to realize the reversible self-assembly and disassembly of Au nanovesicles (NVs) driven by pH stimuli with commercially available organic molecules, 4-mercaptobenzonic acid (4-MBA) and oleylamine (OL). Through adjusting deprotonation and protonation of 4-MBA, Au NVs demonstrated a good reversible self-assembly behavior. As a proof-of-concept, Rhodamine B was loaded into the vesicles to demonstrate the reversible pH-responsive controlled release.