Liquid capillarity through porous media can be enhanced by a rational design of hierarchically porous constructs that suggest sufficiently large liquid pathways from an upper-level hierarchy as well as capillary pressure enabled by a lower hierarchy. Here, we demonstrate a material design strategy utilizing a new class of self-assembled soft materials, called bicontinuous interfacially jammed emulsion gels (bijels), to produce hierarchically porous copper, which enables the unique combination of unprecedented control over both macropores and mesopores in a regular, uniform, and continuous arrangement. The dynamic droplet topologies on the hierarchically copper pores prove the significant enhancement in liquid capillarity compared to homogeneous porous structures. The role of nanoscale morphology in liquid infiltration is further investigated through environmental scanning electron microscopy, in which wetting through the mesopores occurs at the beginning, followed by liquid transport through macropores. This understanding on capillary wicking will allow us to design better hierarchically porous media that can address performance breakthroughs in interfacial applications, ranging from battery electrodes, cell delivery in biomedical devices, to capillary-fed thermal management systems.