Polyvinylidene difluoride fibers and composite fibers with Ni-Zn ferrite nanoparticles and rutile nanoparticles were prepared by electrospinning dimethyl formamide (DMF) solutions. To prevent agglomeration, the ferrite nanoparticles were coated with silica, allowing the formation of a stable ferrofluid in DMF as well as the formation of homogeneous fibers. The rutile nanoparticles could be spun with a uniform distribution within the fiber without silica coating. The effects of various solution properties (viscosity and solids loading for composite fibers) and processing parameters (flow rate and voltage) on fiber morphology and diameter were studied to identify a processing window that resulted in the formation of smooth, defect-free fibers. Of the variables examined, fiber diameter was found to be the most strongly dependent on the viscosity of the electrospinning solution. Infrared spectroscopy revealed that the inclusion of well-dispersed nanoparticles in the electrospun fibers enhanced the presence of the ferroelectric phase in the composite fibers.