Blend films based on the poly(epsilon-caprolactone) (PCL) and amphiphilic biodegradable polymer, poly(ethylene glycol) grafted poly(epsilon-caprolactone) (PCL-g-PEG), were prepared with different blend ratios in order to develop new biomedical material. PCL was the main component in the blend. The miscibility and characteristics of the blends were investigated. The crystallization temperature of the blend shifted to high temperatures with an increase of the graft copolymer contents when the homopolymer PCL was the main component of the blend. The PEG side chain in the blend affected the crystallization rate of the PCL crystals in the blend and alternating extinction bands were observed by optical microscopy. The protein adhesion behavior of the film was influenced by the water uptake of the film.