Recently, many studies have investigated additive manufacturing of hierarchical surfaces with high surface area/volume (SA/V) ratios, and their performance has been characterized for applications in next-generation functional devices. Despite recent advances, it remains challenging to design and manufacture high SA/V ratio structures with desired functionalities. In this study, we established the complex correlations among the SA/V ratio, surface structure geometry, functionality, and manufacturability in the Two-Photon Polymerization (TPP) process. Inspired by numerous natural structures, we proposed a 3-level hierarchical structure design along with the mathematical modeling of the SA/V ratio. Geometric and manufacturing constraints were modeled to create well-defined three-dimensional hierarchically structured surfaces with a high accuracy. A process flowchart was developed to design the proposed surface structures to achieve the target functionality, SA/V ratio, and geometric accuracy. Surfaces with varied SA/V ratios and hierarchy levels were designed and printed. The wettability and antireflection properties of the fabricated surfaces were characterized. It was observed that the wetting and antireflection properties of the 3-level design could be easily tailored by adjusting the design parameter settings and hierarchy levels. Furthermore, the proposed surface structure could change a naturally-hydrophilic surface to near-superhydrophobic. Geometrical light trapping effects were enabled and the antireflection property could be significantly enhanced (>80% less reflection) by the proposed hierarchical surface structures. Experimental results implied the great potential of the proposed surface structures for various applications such as microfluidics, optics, energy, and interfaces.