We present a temperature-induced sedimentation/dispersion transition of ionic vesicles in the system of alkyldimethylamine oxide hemihydrochloride (CnDMAO⋅12HCl) with a hydrocarbon chain length of 12–16 (n=12, 14, and 16) and sodium 2-naphthalenesulfonate (NaNphS). The temperature-sensitive sedimentation/dispersion of ionic vesicles took place around a temperature of 50 °C, which was weakly dependent on the alkyl chain length. The combined effect of the thermally induced dissociation of the counterions from the vesicle and a hydrogen bonding between the nonionic and the cationic head groups is likely to be responsible for this unique behavior.