This study presents near-field electrospinning (NFES) on flat and hollow cylindrical process to fabricate permanent piezoelectricity of polyvinylidene fluoride (PVDF)/ multi-walled carbon nanotube (MWCNT) piezoelectric nanofibers. Then the mechanical properties of fibers were measured. PVDF is a potential piezoelectric polymer material combining desirable mechanical, thermal, electrical properties with excellent chemical resistance. The existing researches mostly focused on piezoelectric thin film process. However, the research of characteristic about piezoelectric fiber is little. The methods of measurement of the mechanical properties (Young¡¦s modulus, hardness, and tensile strength¡Belongation) of the electrospun PVDF/MWCN composite nanofiber were carried out by using nano-indention test (MTS Nanoindenter Windows XP System) and tensile test (Microforce Testing System). By setting electric field (1¡Ñ107 V/m), rotating velocity (900 rpm) of the hollow cylindrical glass tube on a motion X-Y stage (2 mm/sec) and PVDF solution concentration (16 wt%), and MWCNT (0.03 wt%), in-situ electric poling, mechanical stretching and morphology of PVDF nanofiber were demonstrated. After the experiments of nano-indention test and tensile strength test, it is suggested that the good mechanical properties in NFES on cylindrical process. The results show that the mechanical properties of composite nanofiber are better than the conventional NFES process. The Young¡¦s modulus of 16% PVDF fiber prepared by cylindrical process is 0.89 GPa and hardness is 26.5 MPa. The mechanical properties were increased 56.2% and 49.4% after adding 0.03% of MWCNT, corresponding to 1.39 GPa and 39.6 MPa. The tensile strength was increased 32.7% and elongation at breaking point was increased 35% after adding 0.03% MWCNT.