<p>Electrospinning is the most cost-effective technique for fabricating non-woven mats of fibre ranging in size from nano to submicron. Several polymers have been effectively electrospun in ultrafine fibre form by the electrospinning technique, either in melt or solution form. This study analysed the effect of various electrospinning parameters, such as solution concentration, applied voltage, flow rate, conductivity and solvent types, on the morphology of ultra-high molecular-weight polyethylene (UHMWPE) fibres. Different solvents, such as decalin, p-xylene, p-cymene and cyclohexanone, have been used in various combinations to study the effects of solvent types. It has been observed that the concentration of the solution is critical for producing fibres instead of beads during the electrospinning process. A higher ratio of decalin in a mixture with cyclohexanone leads to the merging of fibres due to insufficient solvent evaporation, which results in solvent entrapment. Conversely, increasing the proportion of cyclohexanone enhances the solution conductivity, reducing the fibre diameter. At a 2 wt% solution concentration of UHMWPE, a smooth and uniform fibre can be produced using a 70:30 ratio of decalin to cyclohexanone, with a flow rate of 1 µl s^–1 and an applied voltage of 15 kV. This combination of electrospinning parameters represents the optimal conditions for generating defect-free fibres.</p>