One-dimensional (1D) mesoporous nanofibers (NFs) have recently attracted tremendous interest in different fields, in virtue of their mesoporous structure and 1D geometry. However, conventional electrospinning, as a versatile approach for producing 1D nanostructures, can only fabricate solid NFs without pores or with a microporous structure. In this review, we focus on the extensions of the electrospinning technique to create 1D mesoporous fibrous structures, which can be categorized into: (i) foaming-assisted, (ii) phase separation-induced, (iii) soft-templated, and (iv) monomicelle-directed approaches. Special focus is on the synthesis strategies of 1D mesoporous NFs, and their underlying mechanisms, with looking into the control over pore sizes, pore structures, and functionalities. Moreover, the structure-related performances of mesoporous NFs in photocatalysis, sensing, and energy-related fields are discussed. Finally, the potential challenges for the future development of 1D mesoporous fibers are examined from the viewpoint of their synthetic strategies and applications. Four extended electrospinning techniques to construct mesoporous nanofibers were summarized and the structure related performances in photocatalysis, sensors, and energy related fields were highlighted.