SiO2 nanofibers have been produced by the electrospinning method by two different approaches: direct spinning of silica precursor-containing nanofibers and spinning of polymer nanofibers followed by sol–gel silica coating. After pyrolysis of the resulting materials, both methods yield silica nanofibers. We extend this work by coating the silica nanofibers with AlN films using a reactive magnetron sputtering technique. Substrate temperature, input gas composition and radio frequency (rf) power are the critical operating parameters for the formation of different crystal structures of the AlN shells. The AlN/SiO2 core-shell heterostructures demonstrate that electrospinning has the potential to produce low-mass, high-surface-area flexible nanofibers for potential space-based applications.