Olefin copolymers are of increasing scientific interest due to their important application potential. Liquid chromatography can deliver important information, especially on their molecular structure. In particular, liquid chromatography at critical conditions (LCCC) is of interest because, in this chromatographic mode, the elution is molar mass independent for a given repeat unit. LCCC is conducted at conditions where the entropic effect of size exclusion is equal to the enthalpic effect of interaction between the macromolecules and the stationary phase and can be used to separate copolymers as well as some homopolymers containing one single repeat unit but having different end groups. For the first time, critical conditions for linear PE were experimentally identified by using porous graphite (Hypercarb (TM)) as the stationary phase, and either 1-decanol/ortho-dichlorobenzene (ODCB), 1-decano1/1,2,4-trichlorobenzene (TCB), ndecane/ODCB, or n-decane/TCB as the mobile phase at 160 degrees C. The identified critical conditions for PE using the above approach in the above solvents have been verified to be correct, barring slight deviations, by two different techniques which were previously used to determine critical conditions for polymers soluble at ambient temperature. The critical conditions for polyethylene were applied to separate statistical copolymers of ethylene/1 -octene with similar molar mass. (C) 2013 Elsevier Ltd. All rights reserved.