It is quite challenging to investigate the dynamics of coordination-driven self-assembly due to the existence of multiple intermediates and many possible processes. By taking advantage of the high sensitivity and efficiency of fluorescence-resonance energy transfer (FRET), FRET was successfully employed to real-time monitor the dynamic behavior of coordination-driven self-assembly. The Forster energy transfer efficiencies and kinetic aspects of a series of discrete, well-defined metallacycles have been determined. Moreover, the dynamic characteristics of these supramolecular assemblies, such as the dynamic ligand exchange, anion-induced disassembly and reassembly, and stability in different solvents, have been investigated by using FRET.