The search for the development of nanostructured materials has led to the study of the properties of their precursors. For the production of nanofibers by the electrospinning process, it is necessary to determine the rheological parameters of the precursor solutions. Since these properties can be influenced by the processing variables and chemical composition of the polymer, this study aims to elucidate the effect of the addition of vinyl monomers in the formulation of nanofibers based on polyacrylonitrile and to determine the optimal parameters for the production of the precursor polymer solution. The effects of temperature and addition of vinyl monomers were evaluated by rheometry, from the analysis of the variation of the viscosity of the solutions, and by microscopy, the morphology of the nanofibers produced. It was observed that the increase in the temperature used to produce the solutions improves the fibers’ properties. Still, there is a relationship between the time of exposure of the polymeric solution to the temperature and the homogeneity of the fibers, which cannot exceed 45 min. The addition of vinyl monomers, to produce PAN-PVA co-polymeric fibers, increases the conductivity and reduces the viscosity of the solutions, resulting in more refined and homogeneous fibers.