Macromolecules with fluoroalkyl group are promising as anti-fouling materials. In the work, a series of poly-caprolactone grafted poly(octafluoropentyl methacrylate-co-hydroxyethyl methacrylate)s (PCL-PFHs) were synthesized as additives to change the surface properties of poly(L-lactic acid) (PLLA). The synthesized products were characterized with (HNMR)-H-1 and GPC. PCL-PFH and PLLA were immiscible in blend, but PCL-PFH micro-particles could immerse uniformly in PLLA substrate. The molar ratio of [OFPA]/[HEMA] in PFH and blend ratio of PCL-PFH/PLLA played a key role in changing the surface properties of PLLA blend. When the molar ratio and blend ratio were 4/1 and 10/90 respectively, the surface tension of PLLA blend lowered to 19.57 mN m(-1), and it inhibited BSA adhesion effectively during protein adsorption process. At the same time, PLLA blend presented good hydrolytic stability. PCL-PFH also toughened PLLA, and the tensile strength and elongation at a break were 37.0 MPa and 126.1%. Then this work would built a new bridge between PLLA materials and biomedical engineering.