In this article, we describe a microfluidic approach to fabricate hollow and core/sheath nanofibers by electrospinning. Key benefits in using microfluidic devices for nanofiber synthesis include rapid prototyping, ease of fabrication, and the ability to spin multiple fibers in parallel through arrays of individual microchannels. Hollow poly (vinylpyrrolidone) (PVP) + titania (TiO2) composite and core/sheath polypyrrole (PPy)/PVP nanofibers of the order of 100 and 250 nm, respectively, were successfully fabricated using elastomeric microfluidic devices. Fiber characterization was subsequently carried out using a combination of scanning electron microscopy and transmission electron microscopy.