A hierarchical structure featuring both nano- and macro- structure has emerged as prospective candidates for the application requiring high flow rates and specific surface area. A unique physical and mechanical behavior could be discovered by designing a special structure. A random orientated nanoporous copper thin film coated on a three-dimensional (3D) microporous periodical octet-truss lattice was utilized as a hierarchical structure to evaluate the mechanical and catalytic behaviors. Nanoporous copper films with ligament size ranging from 16 to 28 nm were synthesized using magnetron co-sputtering CuAl alloy films and subsequent dealloying process, while the octet-truss with a pore size of 120 μm was fabricated by digital light processing. The yield strengths of the octet-truss lattice with nanoporous Cu (L-NPC) films are 3 times higher than those of low-density bulk Cu or Cu films predicted by the Gibson-Ashby equation. The current densities and electrochemical surface area of the l-NPC films are also 10 times higher than those of octet-truss lattice with solid Cu films or NPC films coating on a two-dimensional substrate. In addition to the nano-scale pore size effect, the 3D polymer structure produced a high curly surface for NPC films to attach on the truss which could be the reason for the different mechanical and electrochemical behaviors.