A novel approach to property enhancement Of Poly(L-lactic acid) (PLLA) through the use of perfluoropolyether (PFPE) enchainment is described. Segmented copolymers (FluoroPLA) exhibit tailored surface properties with reasonably high molecular weights and low polydispersities compared to PLLA alone using standard ring-opening polymerization procedures in the presence of tin catalysts. Low loadings of PFPE content (ca. 1 - 5 wt %) decreases surface energies compared to PLLA from 35 to 38 to 15 - 18 mN/m(2), similar to values reported for poly(tetrafluoroethylene). Ultimate strain studies of FluoroPLA fibers and films have shown a dramatic increase (> 300% elongation) over PLLA. This new class of polymer may further expand the use of renewable resources in a variety of applications such as flame retardants, chemical resistant fibers and/or fabrics with tailorable surface energies and wetting properties.