The effects of the crystallization temperatures of poly(ethylene succinate) (PES) on the crystallization behavior of poly(ethylene oxide) (PEO) in their blends were investigated by means of differential scanning calorimetry, atomic force microscopy, and laser confocal fluorescent microscopy. It was found that confined and fractional crystallization of PEO takes place in the PES/PEO blends at all blend ratios if PES is crystallized at higher crystallization temperatures. And morphological observation gives a direct evidence of the different location distribution of PEO, resulting in the confined and fractional crystallization behavior.