The preferential crystallization is an old technology to separate racemic mixtures of conglomerate forming systems into the pure enantiomers due to the advantages of obtaining directly a solid product. Unfortunately, only a small part of all chiral systems belong to that group. Thus until now, the applicability of preferential crystallization is strongly limited. The majority of the chiral systems forms racemic compound forming systems, where from the thermodynamic point of view preferential crystallization is not feasible to provide the pure enantiomers. However, an extension of the applicability of preferential crystallization to racemic compound forming systems would significantly widen the potential of this separation technique. The innovative part of this work is to demonstrate the general feasibility of the preferential crystallization in case of racemic compound forming systems. As chiral model systems threonine, mandelic acid, propranolol hydrochloride and methionine were chosen. In the experimental part at first systematic studies of the binary and ternary phase diagrams as well as the metastable zone widths and the nucleation behaviors were carried out. Based on this the preferential crystallization experiments were planed and performed. The gained product purities, productivities and yields were summarized for the discussion of the economic potential of the separation strategy. Finally, a “decision tree” is represented which allows finding an efficient resolution strategy in case of new separation problems.