Electrospinning is a straightforward method to produce sub-micrometer or nanoscale fiber. Polycaprolactone (PCL), an important polymer in biomedical applications, has been electrospun in several solvent systems. N, N-dimethylformamide (DMF) is often used as an additive in the solvent system to prepare PCL nanofibers. The adding of the DMF changes the physical properties of the solution. To trace and understand the influence of these changes on the jet formation as well as the resultant fibers morphologies, a model of jet perturbation based on the Plateau-Rayleigh Instability theory was established to explicate the formation of the particles/fibers and some experiments for testing the solution properties and fibers morphologies were carried out. With the adding of DMF in dichloromethane (DCM)/DMF mixed solvents, the solution surface tensions increase while solution viscosities decrease, which triggers the change of electrospinning to electrospraying in general. However, according to the obtained results, the addition of the DMF makes it easier to induce the transformation of particles electrospraying to fibers electrospinning with smaller diameter. This is attributed to the higher dielectric constant, lower vapor pressure, and higher electric conductivity of DMF. The theoretical model and experimental results strengthen the relations of solution properties, jet moving behaviors, and the resultant fiber morphologies.