A statically non-wetting highly hydrophobic fibrous surface was generated from biphenyl perfluorocyclobutyl aryl ether polymer (BP-PFCB) by electrospinning. The optimization of solution parameters, which include concentration of the solution and number-average molecular weight of the polymer, was followed by optimization of the instrumental parameters, which include flow rate, inter-electrode voltage and inter-electrode distance. Varying these parameters resulted in different degrees of hydrophobicity on the generated surfaces. The degree of hydrophobicity was determined by measuring static water contact angles. The effects of these variations in electrospinning parameters on the thickness of the fibers constituting the surface were also observed. It was found that the hydrophobic nature of the electrospun fibrous surface of BP-PFCB depended on two factors: fluorine concentration and thickness of the fibers. During the optimization of the parameters, three different morphological regimes, namely beads, beaded fibers and fibers, were observed. The fine tuning of electrospinning parameters eventually produced a statically non-wetting, highly hydrophobic surface which predominantly consisted of an intricate network of nanoscale fibers. (C) 2013 Society of Chemical Industry