In order to obtain satisfied spherical agglomerated product and overcome the incomplete removal of the impurity during the traditional spherical agglomerated process, a new strategy incorporating the spherical agglomeration technique and the drowning-out crystallization process, by which the impurities call be efficiently removed, was performed. A triangular phase diagram showing the phase equilibrium of tertiary solvent mixtures used in the process of spherical crystallization was constructed and the real-time spherical crystallization process was investigated by means of particle vision measurement and microscopy. The operation conditions, including the chloroform content, temperature of the system, and agitation speed, were also investigated in order to optimize the spherical crystallization process. The results of HPLC and GC indicated that the purity and residual solvents of the experimental agglomerated product can meet the requirements for use. Simultaneously, their bulk density, flowability, and compressibility are far better than the dispersed crystals. The agglomerated particle size was easily controlled by adjusting the chloroform Content. temperature of the system, and agitation during Spherical crystallization. Especially, the chloroform content is Much more important than temperature and agitation in determining agglomerated particle size.