The structure formation by liquid-liquid(L-L) phase separation coupled with crystallization in isotactic polypropylene(i-PP) solutions was investigated by temperature-jump experiment. A series of dialkyl phthalates with a different number of carbon atoms in the alkyl chain was used to control the interaction between polymer and solvent. Various thermal quench conditions were applied to the i-PP solutions to control systematically L-L phase separation and crystallzation. A slow crystallization elongates the liquid droplets in the radial direction of a spherulite. A rapid crystallization under the deep quench locks-in the growth of L-L phase separation. These results indicate that the extent of L-L phase separation which exists below melting point can be successfully controlled through the proper selection of solvent and thermal conditions.