In this work, we used poly(L-lactide)-block-poly(ethylene glycol) (PLLA-b-PEG) copolymer thick films to investigate the effect of crystallization on surface segregation, surface crystal orientation, and morphology by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), reflection optical microscopy (ROM), and two-dimensional grazing incident wide-angle X-ray scattering (2D GIWAXS) methods. ATR-FTIR results indicated that the surface fraction of PLLA block increased from 0.48 to 0.79 when T-c,T-PLLA increased from 70 to 110 degrees C. Polarized ATR-FTIR and 2D GIWAXS results indicated that PLLA crystal lamellae preferentially oriented parallel to the film surface with increasing T-c,T-PLLA. The surface crystallinity of PLLA was almost independent of T-c,T-PLLA, while the surface crystallinity of PEG decreased with increasing T-cPLLA. On the basis of surface crystal orientation and crystallization kinetics, we suggested that the excess of PLLA component at the surface was mainly dominated by a coupling effect of crystallization behavior and surface segregation.