This study investigated the surface structure of fluorocarbon end-capped l-poly(lactide)s (F-PLLA) with different fluorocarbon lengths by electron spectroscopy for chemical analysis (ESCA). Fluorocarbon chains of three lengths (F(CF2)n(CH2)2, where n = 6, 8, and 10) have been synthesized as the terminal group to PLLA. Angular dependent ESCA revealed that the fluorocarbon groups are segregated at the surface. Further, the results show the surface coverage of fluorocarbon groups rapidly increases with increasing the length of fluorocarbon end groups (synergy effect). The surface composition of F-PLLAs can be controlled by changing the length of fluorocarbon.