Multiwalled carbon nanotubes (MWNT) were functionalized with poly(L-lactic acid) (PLLA) with different molecular weights using a "grafting to" technique. The oxidized MWNT (MWNT-COOH) were converted to the acyl-chloride-functionalized MWNT (MWNT-COCl) by treating them with thionyl chloride (SOCl2) and reacting them with PLLA to prepare the MWNT-g-PLLA. FTIR and Raman spectroscopy revealed that the PLLA was covalently attached to the MWNT, and the weight gain due to the functionalization was determined by thermogravimetric analyses (TGA). The Raman signals of the MWNT were greatly weakened as a result of the PLLA grafting. The morphology of the grafted PLLA was examined by using SEM and TEM. The amount of grafted PLLA depended on the molecular weight of the PLLA. The PLLA coated on the MWNT became thicker and more uniform with increasing PLLA molecular weight from 1000 to 3000. However, the amount of grafted PLLA became lower when the molecular weight of PLLA was further increased to 11,000 and 15,000, and the PLLA attached to the MWNT showed a squid leglike morphology forming blobs and leaving much of the MWNT surface bare.