A new type of bolaamphiphile bearing bipyrimidine (bpym-8) has been designed and synthesized. The bipyrimidine moiety allows for metal-ligand coordination, thereby influencing the self-assembly of the bolaamphiphile. Before coordination, bpym-8 self-assembles in water to form spherical aggregates. An interesting finding is that the coordination of the Cu(II) ion with bipyrimidine can induce the assembly of bpym-8 to change from spheres to clustered aggregates. It should be noted that the assembly of bpym-8 can be reversibly converted back by removing the Cu(II) ion from the coordination. This study presents a new type of bolaamphiphile that is able to coordinate with metal ions, which may provide a new clue in fabricating reversibly tunable supramolecular nanomaterials.