The need to biofunctionalize polymer surfaces for targeted bio-related applications continues to grow, and efforts designed to meet this need rely heavily on surface grafting or polymerization. in this study, we provide a viable alternative by demonstrating that the peptide segment of a polymer-peptide conjugate can be selectively driven to the surface of polymer nano/microfibers during electrospinning due to contrast in polarizability. Judicious choice of the polymer sequence in the conjugate permits use of the conjugate with compatible fiber-forming polymers. Here, we use a water soluble poly(ethylene oxide)-containing conjugate in combination with a hydrophobic thermoplastic, poly(methyl methacrylate). Surface enrichment is measured by X-ray photoelectron spectroscopy, and fiber morphology is investigated by electron microscopy. Microfibers generated from the blends examined here are largely resistant to long term water immersion and are thus suited as support scaffolds or filtration membranes.