Hollow poly (vinylpyrrolidone) (PVP) + TiO(2) and polypyrrole (core)/PVP (sheath) nanofibers were successfully electrospun using hydrodynamic fluid focusing. Utilizing a two-dimensional fluid focusing technique previously applied to aqueous solutions, intersecting microchannels cast in (poly)dimethylsiloxane were utilized to dynamically center core fluids in immiscible sheath fluids prior to electrospinning at the channel outlet. Advantages of using microfluidic channel networks for the electrospinning of composite nanofibers include spatiotemporal control over input reagents, ease of fabrication and the ability to focus the core stream into sheath layer without the need of complex co-annular nozzles.