The crystallization behavior and morphology of the crystalline-crystalline poly(ethylene oxide)-poly(epsilon-caprolactone) diblock copolymer (PEO-b-PCL) was studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), small-angle X-ray scattering (SAXS), and hot-stage polarized optical microscope (POM). The mutual effects between the PEO and PCL blocks were significant, leading to the obvious composition dependence of the crystallization behavior and morphology of PEO-b-PCL. In this study, the PEO block length was fixed (M-n = 5000) and the weight ratio of PCL/PEO was tailored by changing the PCL block length. Both blocks could crystallize in PEO-b-PCL with the PCL weight fraction (WFPCL) of 0.23-0.87. For the sample with the WFPCL of 0.36 or less, the PEO block crystallized first, resulting in the obvious confinement of the PCL block and vice versa for the sample with WFPCL of 0.43 or more. With increasing WFPCL, the crystallinity of PEO reduced continuously while the variation of the PCL crystallinity exhibited a maximum. The long period of PEO-b-PCL increased with increasing WFPCL from 0.16 to 0.50 but then decreased with the further increase of WFPCL due to the interaction of the respective variation of the thicknesses of the PEO and PCL crystalline lamellae. Only the PEO spherulites were observed in samples with WFPCL of 0.16-0.36 by POM, in contrast to only the PCL spherulites in samples with WFPCL of 0.56-0.87. For samples with WFPCL of 0.43 and 0.50, a unique concentric spherulite was observed. The morphology of the inner and outer portions of the concentric spherulites was determined by the PCL and PEO spherulites, respectively. The growth rate of the PEO spherulites reduced rapidly with increasing WFPCL from 0 to 0.50. However, when increasing WFPCL from 0.43 to 0.87, the variation of the growth rate of the PCL spherulites exhibited a maximum rather than a monotonic change.