We synthesized a tetrameric amphiphilic molecule (1) based oil a calix[4]arene building block that self-assembled into different tunable and stable aggregation structures at different pH values in aqueous solution. The amphiphilic calix[4]arene molecule (1) formed a spherical structure at pH 3. However, 1 formed a hollow necklacelike structure of 500 rim diameter at pH 7. These results indicate that the self-assembled morphologies of 1 are strongly dependent on pH values. In addition, a 3D dendritic silver nanostructure was obtained by the self-assembly of 1 at pH 7.