Aluminum nitride (AlN) hollow nanofibers were synthesized via plasma-enhanced atomic layer deposition using sacrificial electrospun polymeric nanofiber templates having different average fiber diameters (~70, ~330, and ~740 nm). Depositions were carried out at 200°C using trimethylaluminum and ammonia precursors. AlN-coated nanofibers were calcined subsequently at 500°C for 2 h to remove the sacrificial polymeric nanofiber template. SEM studies have shown that there is a critical wall thickness value depending on the template's average fiber diameter for AlN hollow nanofibers to preserve their shapes after the template has been removed by calcination. Best morphologies were observed for AlN hollow nanofibers prepared by depositing 800 cycles (corresponding to ~69 nm) on nanofiber templates having ~330 nm average fiber diameter. TEM images indicated uniform wall thicknesses of ~65 nm along the fiber axes for samples prepared using templates having ~70 and ~330 nm average fiber diameters. Synthesized AlN hollow nanofibers were polycrystalline with a hexagonal crystal structure as determined by high-resolution TEM and selected area electron diffraction. Chemical compositions of coated and calcined samples were studied using X-ray photoelectron spectroscopy (XPS). High-resolution XPS spectra confirmed the presence of AlN.