In this study, we report niobium (Nb) with hierarchical porous structure produced by a one-pot, HF-free electrochemical etching process. It is proved experimentally that a well-defined hierarchical porous structure is produced from the combination of a limited repetition of pulse etching and high concentration of aggressive anion (i.e., SO 4 2-), which results in hierarchical pores with high order over 3. A formula is derived for the surface area of porous Nb as a function of the hierarchical order of pores while the experimental surface area is estimated on the basis of the electrochemical gas evolution rate on porous Nb. From the comparison of the theoretical and experimental surface areas, an in-depth understanding was gained about porous structure produced in this work in terms of the actual pore shape and hierarchical pore order.