The separation mechanism of charged fluorophore (aminopyrenetrisulfonate)-labeled maltooligosaccharides with α1-4 linkages was studied in polyethylene oxide (PEO) solutions (MW 300 000 Da) with special interest to possible analyte and/or network deformations as well as potential solute-matrix interactions. The electrophoretic mobilities of the 8-aminopyrene-1,3,6-trisulfonate-labeled maltooligosaccharides were found proportional with their MW(-2/3) . The Arrhenius function was used to determine the activation energy needed by the labeled sugars to migrate through the separation media. With increasing solute size, the activation energy (Ea ) values decreased in polymer concentrations above the entanglement threshold of the PEO, while showed apparently independent function at the entanglement threshold. The observed phenomenon was considered as a result of solute-matrix interaction, which could be alleviated by the addition of an organic modifier to the BGE.