A method for modifying an ePTFE surface by plasma immersion ion implantation includes the steps of providing an ePTFE material in a chamber suitable for plasma treatment; providing a continuous low energy plasma discharge onto the sample; and applying negative high voltage pulses of short duration to form a high energy ion flux from the plasma discharge to generate ions which form free radials on the surface of the ePTFE material without changing the molecular and/or physical structure below the surface to define a modified ePTFE surface. The step of applying the high voltage pulses modifies the surface of the ePTFE without destroying the node and fibril structure of the ePTFE, even when the step of applying the high voltage pulses etches and/or carburizes the surface of the ePTFE. The modified surface may have a depth of about 30 nm to about 500 nm. The ions are dosed onto the ePTFE sample at concentrations or doses from about 1013 ions/cm2 to about 1016 ions/cm2.