Fibers of poly(vinylidene fluoride) (PVDF) filled with multiwalled carbon nanotubes (MWCNTs) were prepared by solution blow spinning (SBS). The influence of the MWCNTs on the surface morphology and mechanical behavior of single fibers was studied. The morphology of the materials prepared and the dispersion of the MWCNTs within the polymer were studied by optical microscopy (OM) and transmission electron microscopy (TEM), while atomic force microscopy (AFM) was used to inspect the topography of single fibers and to perform nanoindentation tests. OM and TEM images indicated a good dispersion of the MWCNTs within the PVDF. AFM images evidenced clear changes in the topography of the blow-spun fibers when the MWCNTs were present in the polymer. A greater amount of MWCNTs in the PVDF led to more heterogeneous fiber surfaces. The nanoindentation force curves revealed that the stiffness was practically constant along the fibers, which indicated that the mechanical response was homogeneous and, in turn, an even distribution of the MWCNTs. The incorporation of the MWCNTs produced a mechanical reinforcement of the PVDF fibers, showing increases of 31% and 49% in the elastic modulus when 1% and 5% by weight of MWCNTs were added to the polymer, respectively.