A novel and facile bottom-up strategy for preparing core-shell nanofibers with selectively localized carbon nanotubes was developed by using hierarchical composite micelles of crystalline-coil copolymer and carbon nanotubes as the building blocks. An amphiphilic di-block copolymer of poly (p-dioxanone) (PPDO) and PEG (polyethylene glycol) functionalized with pyrene moieties at the chain ends of PPDO blocks (Py-PPDO-b-PEG) was designed for constructing composite micelles with multiwalled carbon nanotubes (MWCNTs). The self-assembly of Py-PPDO-b-PEG and MWCNTs was co-induced by the crystallization of PPDO blocks and the π-π stacking interactions between pyrene moieties and MWCNTs, resulting in composite micelles with “shish-kebab”-like nanostructure. A mixture of composite micelles and polyvinyl alcohol (PVA) water solution was then used as the spinning solution for preparing electrospun nanofibers. The morphologies of the nanofibers with different composition were investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM). The results suggested the MWCNTs selectively localized in the core of the nanofibers of MWCNTs/Py-PPDO-b-PEG/PVA. The alignment and interfusion of composite micelles during formation of nanofibers may confine the carbon nanotube in the hydrophobic core region. In contrast, the copolymer without pyrene moieties cannot form composite micelles, thus these nanofibers showed  selective localization of MWCNTs in the PVA shell region.