Non-aqueous Taylor dispersion analysis (TDA) was used for the size-characterization of natural and synthetic polyisoprenes (4¿×¿103–2¿×¿106¿g/mol molar mass). Not only the weight-average hydrodynamic radius (Rh), but also the probability distribution of the hydrodynamic radius, were both derived from the Taylorgrams by a simple integration of the elution profile and by a more sophisticated constrained regularized linear inversion of the Taylorgram, respectively. Results in terms of size characterization (hydrodynamic radii between 2 and 100¿nm) were compared to size exclusion chromatography coupled to a refractive index-based mass detector. Multimodal size distributions were resolved by TDA for industrial and natural polyisoprenes, with the advantage over the chromatographic technique that, in TDA, there is no abnormal elution of microaggregates (hydrodynamic radii¿~¿40–50¿nm). Considering the importance and the difficulty of characterizing polyisoprene microaggregates, TDA appears as a promising and simple technique for the characterization of synthetic and natural rubber.