Bundle membranes were made by electrospinning poly(L-lactide) (PLLA) and PLLA/poly(ethylene glycol) (PEG) using the ionic properties of diclofenac sodium (DS), lidocaine hydrochloride (LHC), benzalkonium chloride (BC), and combinations thereof. The self-bundling of the fibers was initiated by using a designed grounded multi-needle electrode. Computer simulations on the electrostatic field distribution depended on the multi-needle position with respect to a grounded rotating drum collector which allowed the optimal arrangement of the electrospinning component set-up to obtain bundles. The combination of the ionization of the drugs as well as the utilization of the multi-needle electrode allowed the successful preparation of a series of mono-(DS, LHC, or BC), bi-(DS/LHC), and three-(DS/LHC/BC) drug(s)-loaded bundle membranes. Based on the Fourier transform infrared spectra, the drug systems were incorporated into the fibrous materials. The microbiological tests confirmed that the PLLA/PEG bundle membranes containing BC (10 wt%), DS (30 wt%), DS/LHC (DS, 30 wt%; LHC, 30 wt%), and DS/LHC/BC (DS, 15 wt%; LHC, 15 wt%; and BC, 10 wt%) exhibited antibacterial activity against the pathogenic microorganism Staphylococcus aureus.