A series of new functional poly(ethylene-co-vinyl alcohol)-g-polystyrene graft copolymers (EVAL-g-PS) with controlled molecular weight (M-n=38,000-94,000 g mol(-1)) and molecular weight distribution (M-w/M-n=2.31-3.49) were synthesized via a grafting from methodology. The molecular structure and component of EVAL-g-PS graft copolymers were confirmed by the analysis of their H-1 NMR spectra and GPC curves. The porous films of such copolymers were fabricated via a static breath-figure (BF) process. The influencing factors on the morphology of such porous films, such as solvent, temperature, polymer concentration, and molecular weight of poly-mer were investigated. Ordered porous film and better regularity was fabricated through a static BF process using EVAL-g-PS solution in CHCl3. Scanning electron microscopy observation reveals that the EVAL-g-PS graft copolymer is an efficient compatibilizer for the blend system of low-density polyethylene/polystyrene. (C) 2015 Wiley Periodicals, Inc.