The electrospinning process was used successfully to fabricate nanofibers of poly(ethylene oxide) (PEO) in which multiwalled carbon nanotubes (MWCNT) are embedded. Initial dispersion of MWCNTs in water was achieved using amphiphiles, either as small molecules (sodium dodecyl sulfate, SDS) or as a high molecular weight, highly branched polymer (Gum Arabic). These dispersions provided separation of the MWCNTs and their individual incorporation into the PEO nanofibers by subsequent electrospinning. The focus of this work is on the development of axial orientations in these multicomponent nanofibers. A theoretical model is presented for the behavior of rodlike particles representing CNTs in electrospinning. Initially the rods are randomly oriented, but due to the sinklike flow in a wedge they are gradually oriented mainly along the stream lines, so that straight CNTs are almost oriented upon entering the electrospun jet. The degrees of orientation of polymer, surfactant, and MWCNT were studied using X-ray diffraction and transmission electron microscopy. Oriented ropes of the nanofibers were fabricated in a converging electric field by a rotating disk with a tapered edge. A high degree of alignment of PEO crystals was found in electrospun nanofibers containing only PEO, as well as PEO/SDS. The latter also exhibited a high degree of alignment of the SDS layers. The axial orientation of PEO and SDS is significantly reduced in MWCNT-containing nanofibers. Transmission electron microscopy (TEM) images indicated that the MWCNTs were embedded in the nanofibers as individual elements, mostly aligned along the fiber axis. Nevertheless, there are also many cases in which the nanotubes appear twisted, bent, or with other irregularities. Comparison of cryo-TEM images of vitrified MWCNT dispersions with TEM images of the raw nanotubes indicated that sonication during the dispersion process may be responsible for the irregularities observed in some of the nanotubes.