In this work, core–shell electrospinning was employed as a simple method for the fabrication of composite coaxial polymer fibers that became hollow ceramic tubes when calcined at high temperature. The shell polymer solution consisted of polyvinyl pyrollidone (PVP) in ethanol mixed with an aluminum acetate solution to act as a ceramic precursor. The core polymer was recycled polystyrene to act as a sacrificial polymer that burned off during calcination. The resulting fibers were analyzed with X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) to confirm the presence of gamma-phase aluminum oxide when heated at temperatures above 700 °C. The fiber diameter decreased from 987 ± 19 nm to 382 ± 152 nm after the calcination process due to the polymer material being burned off. The wall thickness of these fibers is estimated to be 100 nm.