The current study focuses on the electrospinning of chitosan (CHT)/multi walled carbon nanotubes (MWNTs) composite nanofiber using a highly stable dispersion. The acetic acid (1–100%) and trifluoroacetic acid/dichloromethane (TFA/DCM 70: 30) was tested as solvent, and the TFA/DCM (70 : 30) is most preferred for fiber formation process with acceptable electrospinnability. Moreover, a new protocol was used to establish proper technique for preparation of electrospinning solution. FT-IR spectroscopy utilized to infer the extent of interaction between CHT polymer chain and MWNT filaments. A quite simple technique was employed to show the stability of electrospinning solution before nanofiber formation process. Scanning electronic microscope (SEM) was employed to show the influence of spinning parameters on surface morphology of electrospun fiber. Under optimized condition, homogeneous and beadfree CHT/MWNTs nanofibers and known physical characteristics were prepared. The formation of conducting nanofibers based on CHT nanocomposites can be considered as a significant improvement in electrospinning of CHT/CNT dispersion. The direct outcome of the current study includes the homogeneous CHT/MWNTs nanofibers with an average diameter of 275 nm and a conductivity of 9×10−5 S/cm. These results are extremely important for further investigation regarding biomedical applications.