Recently, preparation of mesoporous fibers has attracted extensive attentions because of their unique and broad applications in photocatalysis, optoelectronics, and biomaterials. However, it remains a great challenge to fabricate thoroughly mesoporous nanofibers with high purity and uniformity. Here, we report a general, simple and cost-effective strategy, namely, foaming-assisted electrospinning, for producing mesoporous nanofibers with high purity and enhanced specific surface areas. As a proof of concept, the as-fabricated mesoporous TiO2 fibers exhibit much higher photocatalytic activity and stability than both the conventional solid counterparts and the commercially available P25. The abundant vapors released from the introduced foaming agents are responsible for the creation of pores with uniform spatial distribution in the spun precursor fibers. The present work represents a critically important step in advancing the electrospinning technique for generating mesoporous fibers in a facile and universal manner.