A hierarchical surface that includes objects with different sizes, as a result of creating local fields, initiates a large number of effects. Micropores in the composition of macropores, as well as nanoclusters of the substance, were detected by scanning electron and atomic force microscopies on the surface of ZnO/Por-Si samples. An identical fractal dimension for all levels of the hierarchy was determined for these structures, which is associated with the same response to external excitation. Photoluminescence studies have shown the presence of localized levels in the band gap, with the probability of capturing both electrons and holes, which ensures charge transitions between energy bands. Decomposition of the electron paramagnetic resonance (EPR) signal into components made it possible to determine the manifestations of various types of interaction between paramagnetic particles, including the hyperfine structure of the spectrum. The ordering of the structure of the substance as a result of sequential annealing in the range from 300 to 500 °C was revealed in the EPR spectrum. This fact, as well as photo- and gas sensitivity for all types of samples studied, confirms the prospects of using these structures as sensors.