Abstract In this paper, two kinds of ethylene vinyl acetate copolymers (EVA) with different vinyl acetate (VA) contents were modified by plasma technique. The surface hydrophobic recovery and the nanostructure of the samples were evaluated by water contact angle measurement and positron annihilation lifetime spectroscopy, respectively. The water contact angle results indicated that higher VA content would result in faster hydrophobic recovery after plasma modification. The positron annihilation results indicated that two kinds of EVA samples exhibited similar o‐Ps lifetime, and EVA with higher VA content showed higher o‐Ps intensity. The results implied that the faster hydrophobic recovery after plasma modification should be contributed to the easier relaxation of chain segments for the EVA with higher VA content.