Herein, we introduce the concept of pseudoisotope to describe particles which have similar chemistry but different masses. Examples include ligands with different substituents or metal ions with identical charges and similar coordination properties. Mixtures of pseudoisotopes may be used to establish rapidly the nuclearity of polynuclear species by electrospray ionization-mass spectrometry. Pseudoisotope exchange allows the study of the dynamics of polynuclear complexes, and shows these reactions may be surprisingly slow. The evolution of the mass spectra indicates the degree of fragmentation occurring during the exchange.