1D large-pore mesoporous ZnO materials have attracted tremendous attention because of their outstanding properties and promising applications in a wide range of fields. In the present work, we report the fabrication of large-pore mesoporous ZnO nanofibers via an improved electrospinning strategy, namely, the foaming-assisted electrospinning technique, combined with subsequent calcination treatment. The as-fabricated large-pore mesoporous nanofibers were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) specific surface area (S-BET). The obtained products possess well-designed 1D mesoporous nanostructure with high purity and homogeneous large pore sizes. It is found that the content of the foaming agent within the solutions plays a crucial role in the formation of large-pore mesoporous ZnO nanofibers, enabling the growth of the fibers in a controlled manner. The resultant large-pore mesoporous nanofibers exhibit excellent photocatalytic activity and significant stability for hydrogen production compared to conventional solid nanofibers. The present work suggests a facile preparation of the large-pore mesoporous ZnO nanofibers, which may open new doors for their potential applications in photocatalysts.