The size exclusion chromatography of neutral polymers and polymers containing ionic groups was investigated using N,N-dimethylacetamide (DMA) as mobile phase. As reported previously for N,N-dimethylformamide (DMF), acrylonitrile polymers containing charges, even those at terminal end groups, showed markedly small retention volumes and multimodal peaks by refractive index and 280 nm UV detectors. In DMA containing small amounts of LiBr the peaks of the ionic polymers were shifted to small retention volumes while neutral polymers with analogous chemical structures did not show the same behavior. As in the case of DMF the peculiarities observed in DMA were attributed to the formation of supramolecular structures by the interaction of the ionic groups in the polymer and the ionic species from DMA decomposition.