Crystallization and phase behavior in solution-cast thin films of crystalline syndiotactic 1,2-polybutadiene (s-1,2-PB) and isotactic polypropylene (i-PP) blends have been investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM) and field-emission scanning electron microscopy (FESEM) techniques. Thin films of pure s-1,2-PB consist of parallel lamellae with the c-axis perpendicular to the film plane and the lateral scale in micrometer size, while those of i-PP are composed of cross-hatched and single-crystal-like lamellae. For the blends, TEM and AFM observations show that with addition of i-PP, the s-1,2-PB long lamellae become bended and i-PP itself tends to form dispersed convex regions oil a continuous s-1,2-PB phase even when i-PP is the predominant component, which indicates a strong phase separation between the two polymers during film formation. FESEM micrographs of both lower and upper surfaces of the films reveal that the s-1,2-PB lamellae pass through i-PPconvex regions from the bottom, i.e. the dispersed i-PP regions lie on the continuous s-1,2-PB phase. The structural development is attributed to an interplay of crystallization and phase separation of the blends in the film forming process. With solvent evaporation, s-1,2-PB would crystallize first forming the continuous phase, while the segregated i-PP phase accumulated on s-1,2-PB and crystallized subsequently, forming dispersed i-PP regions. (c) 2006 Elsevier Ltd. All rights reserved.