The effect of proline on the prevention of trichloroacetic acid (TCA)‐induced protein precipitation is studied. It is found that proline at high concentrations (>4.0 M) completely prevents TCA‐induced precipitation of hen egg white lysozyme. Other osmolytes such as ethylene glycol, glycerol and sucrose fail to prevent the TCA‐induced precipitation of lysozyme. Viscosity and 1‐anilino‐8‐naphthalene sulphonic acid binding experiments suggest that proline at high concentration forms an ordered supramolecular assembly. Proline is shown to increase the solubility of protein due to formation of such higher order assemblies. A model of the supra‐molecular assembly of proline is proposed and a possible in vivo role of the increased levels of proline under water stress is discussed.