Functional polymers are usually separated by liquid chromatography at critical conditions (LC-CC) using a desorli/adsorli mixture as eluent. In this paper, we describe LC-CC using dimethylformamide (DMF) as pure eluent at 72 degrees C and its application to the analysis of functional polystyrenes. The critical adsorption point is reached by tuning the temperature so that the lack of repeatability is no longer a problem. We analysed several batches of polystyrenes, exhibiting different molecular weights and functionalities. We were able to differentiate di-, mono- and non-functional polystyrenes, bearing carboxylic acid, hydroxyl or nitroxide moieties. The behaviour of these polystyrenes expressed by the experimental results was compared with their behaviour described by the LC-CC theory through the calculation of the effective interaction parameter of each end group. The technique also makes it possible to quantify the fractions of different functional polymers in a blend.