Solutions of five different polymers, namely, polystyrene (PS), polyacrylonitrile (PAN), polyhydroxybutrate (PHB), poly(D-L-lactic acid) (PLA), and Nylon6, were used to investigate their rheological properties on the electrospinnability. In order to effectively reduce the diameter of electrospun fibers, polymers with higher molecular weights (MW) were needed to develop entangled solutions at much lower concentrations and with viscosities as low as that of a pure solvent. A minimum polymer concentration 1.0-2.0 times larger than the entanglement concentration was required to prepare the bead-free fibers. Using this strategy, uniform PS fibers with the lowest ever diameter of similar to 15 nm were successfully obtained using an MW of 3 x 10(7) g/mol at a concentration of 0.1 vol.%. For a given electrospinning solution, processing variables of low flow-rate (Q) and high voltage (V) were desirable in obtaining fibers with small diameters. However, Q and V were correlated by a power law relation: V similar to Q (a), wherein the exponent a had a value of 0.1-0.4, which was relevant with the solution types. Based on the finite element analysis (FEA), a significant measure of electric field (E) occurred around the needle tip used in the experiment, and its magnitude decayed with increasing distance from the needle end (z): E similar to z (-n). The exponent n was 1.0-2.0, depending on the needle-plate geometry, i.e., needle length, needle diameter (D (o) ), plate diameter, and tip-to-plate distance (H). According to FEA results, H exhibited negligible effects on the electric field in the region of interest, i.e., z/D (o) similar to 1 to 10. Due to the presence of high measures of E at the needle end, approaches to render a shorter and thinner straight jet issuing from the Taylor cone to yield thinner fibers were sought because a more significant jet stretching in the "jet whipping region" can take place. A feasible route to predict the as-spun fiber diameter produced by the manipulation of the electrified jet is provided by experimentally measuring the jet diameter and numerically calculating the electric field for the jet whipping process.