The higher surface area of selectively grown multiwall carbon nanotubes (MWCNTs) and the better proximity of the reactant species in in situ microemulsion polymerization were used to attach the polystyrene (PS) nanoparticles to the outer wall of MWCNTs. Attachment were achieved by replacing surfactant with PS nanoparticles. SEM showed that the MWCNTs and PS nanoparticles were distributed in the composite. High resolution transmission electron microscopy showed successful anchoring of PS nanoparticles to the outer wall of the MWCNTs. In addition, anchoring enhanced the Raman's G/D ratio of the MWCNT and degradation temperature in PS nanoparticles. A mechanism of attachment of PS nanoparticles on the outer wall of MWCNT was proposed. The modified MWCNTs exhibited good durability and dispersability in different organic solvents. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1523-1529, 2009