Polyurethane-eugenol solutions in N,N-dimethyl formamide were electrospun/electrosprayed onto polyurethane-ciprofloxacin biomembranes to obtain drug delivery systems for urinary devices. Following electrospinning/electrospraying, particle-fiber morphology was evidenced by scanning electronic microscope analysis. Contact angle determinations along with surface free energy calculations, moisture diffusion test, and diffusion coefficient determinations were done for polyurethane-ciprofloxacin biomembranes. Determination of bioactive ciprofloxacin release kinetics evidences non-Fickian/anomalous/diffusion mechanism, coupling Fickian diffusion with the relaxation of the polymeric chains within the matrix network. A slight increase in n values for electrospun/electrosprayed coated samples evidenced a behavior closer to a case II transport mechanism with zero-order kinetics. The biological activity of the electrospun/electrosprayed polyurethane membrane samples tested against Staphylococcus aureus, Sarcina lutea, Bacillus cereus, Bacillus subtilis, Escherichia coli, and Pseudomonas aeruginosa showed comparable antibacterial activity with standard ciprofloxacin.