We report the synthesis, morphology, and the field effect transistor (FET) characteristics of the crystalline diblock copolymers of poly(3-hexylthiophene) and syndiotactic polypropylene (P3HT-b-sPP). Four diblock copolymers with various sPP block lengths, P3HT(16K)-b-sPP(3K) (P1), P3HT(16K)-b-sPP(6K) (P2), P3HT(16K)-b-sPP(9K) (P3), and P3HT(16K)-b-sPP(14K) (P4), were prepared by the click coupling of N-3-capped sPP and ethynyl-capped P3HT. The stereo-regular crystalline block sPP developed different types of molecular stacking structures and led the P3HT domains to pack lamellar edge-on structure with improved charge transporting characteristics, as evidenced by the grazing incidence wide-angle X-ray scattering (GIWAXS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The FET hole mobilities of P1-P3 thin films were 4.15 x 10(-3), 4.16 x 10(-2), and 3.95 x 10(-3) V-1 s(-1), respectively, which were up to 1 order of magnitude higher than that of the parent P3HT thin film (1.43 x 10(-3) cm(2) V-1 s(-1)). The crystalline-stereoregular crystalline diblock P3HT-b-sPP demonstrates that using the lattice matching concept could well clarify the molecular stacking structure of conjugated polymer segments in order to further improve the performance of organic electron devices.