further extended through well-designed SERS substrates. [5,6] Although many kinds of SERS substrates have been reported, extensive studies have mainly focused on enhancing the sensitivity by generating more SERS-active sites (commonly known as "hot spots") on the substrates using strategies such as colloidal assembly, lithography technique, and nanoimprinting. [7][8][9][10][11] Besides, the wetting properties of the SERS substrates have recently gained much attention. Typically, the SERS substrates that are covered with noble metals are naturally hydrophilic, which in turn restricts further applications such as trace analysis or single-molecule detection because of the low probability in locating the analyte molecules at SERS-active sites especially for highly diluted solutions. [12,13] To overcome the limitations, many strategies have been reported. For example, Yang et al. developed a method by aggregating target molecules and metal nanoparticles into small regions. [14] A slippery liquid-infused porous surface consisting of a Teflon membrane and a perfluorinated lubricant, which eliminates the adhesion of the droplets, was used. Such a surface was found to lead to a constant water contact angle (WCA) during the solvent evaporation process and enhance the aggregation efficiency of the gold nanoparticles (AuNPs) and the target molecules. In another example, Chen et al. demonstrated a strategy to achieve effective aggregation by applying the coffee ring effect using cellulose nanofibers (CNFs) and AuNPs. [15] Suspended analyte particles were carried and accumulated at the drop edges by the hydrodynamic flow, and eventually, formed ring-shape SERS sensitive regions. The CNF-AuNPs substrates were found to have a wider SERS detection zone (L D ≥ 300 µm) compared with the conventional method (L D ≤ 30 µm), which can be attributed to the unique surface properties. Park et al. also developed a facile protocol by placing the analyte molecules at the SERS-active nanogaps of the nanopillars to achieve high sensitivity. [16] By controlling the surface energy of plasmonic nanopillars through the selective removal process, a wide range of WCA from 165.8° (superhydrophobic surface) to 40.0° (hydrophilic surface) was obtained. Under the optimized wetting conditions, successful detection Surface properties are essential for substrates exhibiting high sensitivity in surface-enhanced Raman scattering (SERS) applications. In this work, novel SERS hybrid substrates using polystyrene-block-poly(methyl methacrylate) and anodic aluminum oxide templates is presented. The hybrid substrates not only possess hierarchical porous nanostructures but also exhibit superhydrophilic surface properties with the water contact angle ≈0°. Such surfaces play an important role in providing uniform enhanced intensities over large areas (relative standard deviation ≈10%); moreover, these substrates are found to be highly sensitive (limit of detection ≈10 −12 m for rhodamine 6G (R6G)). The results show that the hybrid SERS substrates can achieve the simu...