Conventional methods of synthesizing bioglass nanofibers from the sol-gel method can be time consuming and result in substantial material loss during the heat treating process. In this study, we have optimized a direct method to produce sol-gel electrospun bioglass fibers without using a polymer binder system. Advantages of this method include decreased processing time, increased fiber production, and decreased material loss after calcination. The conventional method produced bioglass with nanoscale fiber diameters, while the directly electrospun bioglass displayed multi-scale fibers with the majority of fibers in the micron range. The fiber-size of the conventionally spun bioglass depended on the surfactant amount, with the 5% surfactant solution generating the highest quality fibers. Spectroscopic analyses verified that the bioglass fibers had the same composition, irrespective of the methods. The formation of hydroxycarbonate apatite on the surface of the scaffolds during in vitro biomineralization was confirmed. In vitro cell attachment experiments showed that neither conventionally nor directly spun scaffolds had cytotoxic effects on human mesenchymal stem cells.