The present state of the chromatographic techniques based on differentiation of solutes according to their molecular sizes is briefly surveyed. Attention is centred on high-performance techniques applied to purification and characterization of natural macromolecules, and on discussion of the chromatographic approaches to the determination of the molecular masses and molecular mass distributions of both natural and synthetic polymers. The basic requirements on the selection of the separation system and the experimental conditions are summarized, demonstrated on a few examples and critically evaluated.