Gradient chromatography was applied in order to calculate the composition at elution for different methacrylates on normal phase columns. In addition the composition at elution was determined for polyethyleneoxide on a reverse phase column. It is shown that high molar mass polymers elute for a given homopolymer irrespective of their molar mass at the same eluent composition, which varies only slightly with gradient slope. In general the composition at elution in gradient chromatography is expected to be slightly lower than the true critical composition. For high molar mass polymers we found this composition to be close to the critical composition determined by isocratic experiments. The difference between the composition at elution and the true critical composition for a variety of polymethacrylates and for polyethyleneglycol was found to be only between 0.2 and 5%. Thus, after estimating the composition at elution, only a small number of additional isocratic experiments is needed to find the exact critical composition. (c) 2005 Elsevier Ltd. All rights reserved.