The anion-exchange properties of metal-cation-mediated bridged hybrid mesoscopic material (MBH) are carefully investigated. The results of chemical element analysis, XRD, FT-IR, and TG indicate that both small anions such as CH3COO-, NO3-, and large anion surfactant such as SDS- can be exchanged into MBH easily. All anion sites in MBH are exchangeable, which results in a remarkable anion-exchange capacity of 3.9 mmol g-1. MBH shows reversible phase transitions among nearly hexagonal, lamellar, and amorphous structures when various anions are exchanged, which is assigned to the flexible nature of the alkyl chain in the framework of MBH.