The possibilities to fractionate copolymers with respect to their chemical composition on a preparative scale by means of the establishment of liquid/liquid phase equilibria were studied for random copolymers of styrene and acrylonitrile (SAN). Experiments with solutions of SAN in toluene have shown that fractionation does in this quasi-binary system, where demixing results from marginal solvent quality, take place with respect to the chain length of the polymer only. On the other hand, if phase separation is induced by a second, chemically different polymer, one can find conditions under which fractionation with respect to composition becomes dominant. This opportunity is documented for the quasi-ternary system DMAc/SAN/polystyrene, where the solvent dimethylacetamide is completely miscible with both polymers. The theoretical reasons for the different fractionation mechanisms are discussed.