Concentration-dependent bimodal size distributions (comprised of single-molecule particles and multimolecule clusters) observed by microscopic examination of particles collected during electrospray (ES) of dilute solutions of high molecular weight polymers suggest that chain entanglement can interfere with the droplet subdivisions believed to be intrinsic to the electrospray process. The feasibility of such interference is discussed in the context of the spray model of Kebarle, along with its potential impact on the ES mass spectrometry of macromolecules.