Rodlike samples were made from four kinds of poly(ethylene-co-vinyl alcohol) (EVAL) pellets with different ethylene contents. From these rodlike samples, fibers were produced using a melt-electrospinning system equipped with a CO2-laser melting device. The effects on the fiber diameter of the ethylene content and the moisture regain of the rodlike samples were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were reached: (i) EVAL fibers having an average fiber diameter smaller than 1 mu m can be obtained using the system developed; (ii) the diameter of EVAL fiber is influenced by the ethylene content and the moisture regain of the starting rods; (iii) the laser heating does not greatly decrease the melting point and the molecular weight of EVAL; and (iv) preferred crystal orientation can be seen in electrospun EVAL fibers. (c) 2007 Wiley Periodicals, Inc. J AppI Polym Sci 104: 1368-1375, 2007.