Phase diagrams of biological macromolecules are governed by an appropriate combination of interaction potentials in solution. Repulsive regimes favor solubility, whereas the presence of attractive potentials may induce a variety of phase transitions, including the desired macromolecular crystallization. The forces at work may be analyzed with a combination of small angle X-ray scattering and of numerical treatments. From the results obtained with a variety of model systems, the respective advantages and drawbacks of using monovalent salts or PEGs as crystallizing agents are discussed.