Binary polymer blends of polymethacrylates were separated by liquid chromatography at the critical point of adsorption. By operating at chromatographic conditions corresponding to the critical point of one blend component, the blends were separated regardless of the molar-mass distributions of the components. It was shown that, depending on the polarity of the components, polar or non-polar stationary phases must be used. Operating at the critical point of poly(methyl methacrylate), less polar methacrylates can be analysed using silica gel as the stationary phase and methyl ethyl ketone-cyclohexane as the eluent. For the analysis of polar polymethacrylates at the critical point of poly(decyl methacrylate), a reversed stationary phase and tetrahydrofuran-acetonitrile are a useful combination.