Triblock copolymers made up of poly(ethylene oxide) (PEO) and polylactide (PLA) were synthesized and converted to fibers by the electrospinning process. A two-step in situ-synthesis in bulk was applied to extend PLA-PEO-PLA triblock copolymers with relatively short block length and low molecular weight in order to obtain electrospinnable materials. DL-lactide was polymerized to the hydroxyl chain ends of PEO via the stannous octoate route. Hexamethylene diisocyanate (HDI) was added as chain extender in the second step, leading to poly(ether-ester-urethane) multiblock copolymers. The materials were electrospun from solutions in chloroform. Different concentrations and voltages were analyzed. The ether and ester blocks were varied in their block length and their effects on the fiber morphology was studied. Variations in the electrical conductivity of the chloroform solutions were investigated by adding triethyl benzyl ammonium chloride (TEBAC) in different amounts. Finally, with high quality electrospun PLA-PEO-PEO triblock copolymer fibers mechanical cutting was possible. Copyright (C) 2009 John Wiley & Sons, Ltd.