Ultrathin mesoporous bioactive glass hollow fibers (MBGHFs) fabricated using an electrospinning technique and combined with a phase-separation-induced agent, poly(ethylene oxide) (PEO), are described. The rapid solvent evaporation during electrospinning and the PEO-induced phase separation process demonstrated play vital roles in the formation of ultrathin bioactive glass fibers with hollow cores and mesoporous walls. Immersing the MBGHFs in simulated body fluid rapidly results in the development of a layer of enamel-like apatite mesocrystals at the fiber surfaces and apatite nanocrystals inside the hollow cores. Drug loading and release experiments indicate that the drug loading capacity and drug release behavior of the MBGHFs strongly depends on the fiber length. MBGHFs with fiber length >50 µm can become excellent carriers for drug delivery. The shortening of the fiber length reduces drug loading amounts and accelerates drug release. The MBGHFs reported here with sophisticated structure, high bioactivity, and good drug delivery capability can be a promising scaffold for hard tissue repair and wound healing when organized into 3D macroporous membranes.