Macromolecules with fluoroalkyl group are promising as anti-fouling materials. In the work, a series of polycaprolactone 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 1 HNMR and GPC . PCL-PFH and PLLA were immiscible in blend, but PCL-PFH microparticles 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.