The effects of processing parameters, including solution concentration, viscosity, nozzle diameter, voltage bias and the nozzle to collector distance, on the morphology and diameters of poly(methyl methacrylate) (PMMA) fibers have been systematically investigated, using a unique pump-free electrospinning method. For PMMA solution concentrations less than the critical entanglement concentration, c(e), prolate spheroid-shaped droplets or beads with fibers were formed, whereas at concentrations above c(e), good quality bead-free fibers were formed. Quantitative analysis revealed a linear dependence between the solution viscosity and fiber diameter. Larger fiber diameters were achieved by increasing the nozzle diameter and voltage bias. Increasing the bias voltage has the additional effect of broadening the diameter distribution, as a result of splaying and splitting. By contrast, when the strength of the electrical field was reduced by increasing the distance between the nozzle and collector, the overall fiber diameter was reduced.