The solution electrospinning of polyolefins has not been deeply studied mainly due to the difficulty in dissolving these polymers in appropriate solvents. In this study, composite nanofibers of organically modified montmorillonite/ethylene-octene random copolymer were produced for the first time with a mixture of cyclohexane and xylene as a solvent by solution electrospinning. Montmorillonite was used as an additive to increase the electrical charge density of the polymer solution. The influence of solution and process parameters on the electrospun ethylene-octene copolymer fibers' morphology and diameter was investigated using the design of experiment. Multiple regression analysis was used for the optimization of the electrospinning parameters. Ultrafine fibers, with diameters in the range of 150-350nm were obtained; these nanofibers exhibited an excellent hydrophobicity over a period of 10min as revealed by contact angle measurements.