A simple and unique strategy for preparation of large-compound vesicle (LCV)-encapsulated multiwalled carbon nanotubes (MWCNTs) has been developed, and this involves dispersion of MWCNTs in H-shaped copolymers solution in DMF and encapsulation of MWCNTs with LCVs formed from hydrolysis and polycondensation of -Si(OCH3)(3) groups in the arnphiphilic H-shaped copolymers, (PTMSPMA)(2)-PEG(PTMSPMA)(2). This unique noncovalent approach is nondestructive, and the original structure of MWCNTs remains in the resultant MWCNTs/LCVs nanocomposites. The morphologies of nanocomposites LCVs/MWCNTs are controlled by the chain length ratio (N-PTMSPMA/N-PEG.) of PTMSPMA to PEG. For the H-shaped copolymers with N-PMSPMA/N-PEG <= 1.7, they self-assembled to form LCVs with dense cavities in the presence of MWCNTs in a mixture of DMF/H2O. When this ratio was more than 2.0, the large-compound micelle-wrapped MWCNTs were produced. This approach is potentially useful for preparation of MWCNTs encapsulated with various morphologies of polymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3669-3679, 2009