Carboxylated multiwalled carbon nanotubes (MWNTs) were assembled with poly(allylamine hydrochloride) (PAH) onto decomposable colloidal particles, to subsequently yield hollow microcapsules after core removal. A sandwich structure with MWNTs layer embedded in poly(styrenesulfonate sodium salt) (PSS)/PAH multilayers was designed and constructed on melamine formaldehyde particles. Transmission electron microscopy and confocal microscopy revealed the hollow structure and good dispersity of the resultant microcapsules. The MWNTs were uniformly distributed on the capsule walls.