This paper introduces a modified electrospinning system for biomedical wound-healing applications. The conventional electrospinning process requires a grounded electrode on which highly charged electrospun ultrafine fibers are deposited. Biomedical wound-healing membranes, however, require a very low charge and a low level of remnant solvent on the electrospun membrane, which the conventional process cannot provide. An electrohydrodynamic process complemented with field-controllable electrodes (an auxiliary electrode and guiding electrodes) and an air blowing system was used to produce a membrane, with a considerably reduced charge and low remnant solvent concentration compared to one fabricated using the conventional method. The membrane had a small average pore size (102 nm) and high porosity (85.1%) for prevention of bacterial contamination. In vivo tests on rats showed that these directly electrospun fibrous membranes produced using the modified electrospinning process supported the good healing of skin burns.