Natural rubber particles were separated from its latex and dispersed in CTAB aqueous solution pH8. The particles were used as substrates for admicellar polymerization of polycaprolactone-co-polylactide (PCL-co-PLA). TEM revealed the core-shell structure of PCL-co-PLA shell covered NR core particles. FTIR spectra of the extracted shell layer showed characteristic peaks of PCL and PLA. By fixing the equal amount of co-monomers (50:50 mM caprolactone:lactide), initiator content was varied from 0.5 to 2.0 mM per 100 mM co-monomers. The optical microscope showed good covering of the copolymer shell on the NR particles for all initiator content. FTIR reveals insignificant change in absorption intensity with the initiator content. Thermal properties obtained from TGA test demonstrated the well-superposed thermograms of all samples. Their decomposition temperature at onset was about 349 C. Surface modification is necessary for improving compatibility.