The SEC analysis of polyamide-11 and polyamide-12 can be conducted free of association and aggregation phenomena when hexafluoroisopropanol +0.05 mol/L potassium trifluoroacetate are used as the mobile phase. The calibration of the SEC system can be conducted in different ways. As stationary phases non-polar polystyrene and polar perfluoro silicagel were tested. The investigations showed that the polystyrene gel exhibits hydrophobic interactions with the polyamides while with the silicagel selective interactions were not found. Investigating different options for SEC calibration it was found that conventional PMMA calibration does not yield correct results. The universal calibration approach based on PMMA calibration did not work either. Correct molar masses were obtained when the PMMA calibration curve was corrected with data from polyamide blends using a simplex algorithm. Alternatively, calibration can be conducted with broadly distributed polyamides that were first fully characterized by SEC-MALLS. The resulting molar mass distributions for different sets of polyamides were compared with molar masses that were determined directly by SEC-MALLS and excellent correlation was obtained. (C) 2008 Elsevier Ltd. All rights reserved.