Poly(methyl methacrylate) (PMMA)-polyacrylonitrile (PAN) fibers were prepared using a conventional single-nozzle electrospinning technique. The as-spun fibers exhibited core-shell morphology as verified by transmission electron microscopy (TEM) and atomic force microscopy (AFM). AFM-phase and modulus mapping images of the fiber cross-section and X-ray photoelectron spectroscopy (XPS) analysis indicated that PAN formed the shell and PMMA formed the core material. XPS, thermogravimetric analysis (TGA), and elemental analysis were used to determine fiber compositional information. Soaking the fibers in solvent demonstrated removal of the core material, generating hollow PAN fibers.