Electrospun nanofibers along with multiwalled carbon nanotube (MWNT) become an important issue due to their various engineering applications. Carboxylic acid functionalized multiwalled carbon nanotube (c-MWNT) was successfully embedded into polyvinylpyrrolidone (PVP) matrix, forming polymer nanocomposite nanofibers from an electrospinning process in this study using a custom-made electrospinning apparatus. Initially, the c-MWNT was dispersed well in ethanol using an ultrasonicator. For the electrospinning process of the nanocomposite, c-MWNT dispersion in ethanol and PVP solution were mixed. Surface morphology of the produced c-MWNT/PVP nanofibers was compared with that of pure PVP nanofibers using scanning electron microscopy. The formation and distribution of the c-MWNTs in the nanofibers were also studied by transmission electron microscopy. Alignment of the nanotube in the nanofibers was found to depend on the state of initial dispersion. In addition, it was also found that well-dispersed nanotubes were embedded in the polymer matrix with the alignment along the fiber axis due to the carboxylic acid functionalized MWNT for its good compatibility with the PVP, while the aggregated nanotubes were incorporated as dense entanglement. Raman spectroscopy test was further adopted to characterize the nanofibers.