Hierarchical porous carbons, which contain micropores combined with mesopores and/or macropores, promote mass transport through the macropores/mesopores and increase the accessibility of smaller pores compared with single-sized porous carbons. However, current synthesis procedures cannot fabricate tailored hierarchical carbons with both the freestanding structure and mesoporosity. In this work, electrospun porous hierarchical carbon nanofibers with a macro-two-dimensional monolithic structure were successfully prepared through electrospinning combined with the poly(vinylpyrrolidone) template method. The performance of these nanofibers as electrode materials for supercapacitors and vertical flow-through capacitive deionization for desalination were studied to determine the structural characteristics of the macro-two-dimensional monolithic material. This work provides a general approach for preparing carbons with controlled hierarchical pore structures and new insights into the advanced utilization of carbon materials.