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.