Photocatalysts are currently widely used in various research and industrial fields, from water and air purification to solar energy, from self‐cleaning surfaces to wearable biosensors and electronic devices. Among semiconductors, the growing interest is attracted to gallium oxide, especially β‐Ga2O3, due to the unique physical, chemical (especially acid‐resistance), physical–chemical, photochemical properties, and redox potential. These photocatalysts can be used not only as suspended mixture, but also in the form of films, nanoparticles, and nanofibers. The last one is more challenging due to the high level of surface‐to‐volume ratio, porousness, air and water permeability, and excellent morphological and physical–mechanical properties. Moreover, electrospinning techniques, in comparison with fabrication of nanoparticles, allow to obtain photocatalytic devices without usage of additional carrying base, which simplify the industrial process. However, to date there are limited publications related to the Ga2O3 electrospun nanofibers. The aim of this review is to summarize current results of gallium oxide electrospun nanofibers preparation. Special attention is given to the technological parameters of the electrospinning, the polymer solution receipts, and the properties of such nanomaterials and its potential application. Despite the limited number of publications related to Ga2O3 fibers fabrications, that data collected in this review article demonstrate great potential for practical applications.