Ceramic Fe-Al-O nanofibers with a core-shell architecture were obtained by electrospinning. The fibers consist of an Fe-Al-O core with novel lamellar-like mesopores and an Fe-rich shell. A mechanism of this unique core and shell formation is outlined and confirmed. The described mesoporous nanofibers are highly promising for new research and applications involving catalysis, sensing and absorption of mobile components on the accessible porous core surface.