In this study, we pioneered the synthesis of nanoflower-shaped TiO₂-supported Au photocatalysts and investigated their properties. Au nanoflowers (Au NFs) were prepared by a Na-citrate and hydroquinone-based preparation method, followed by wet impregnation of the derived Au NFs on the surface of TiO₂ nanorods (TNR). A uniform and homogeneous distribution of Au NFs was observed in the TNR + NF(0.7) sample (lower Na-citrate concentration), while their distribution was heterogeneous in the TNR + NF(1.4) sample (higher Na-citrate concentration). The UV-Vis DR spectra revealed the size- and shape-dependent optical properties of the Au NFs, with the LSPR effect observed in the visible region. The solid-state EPR spectra showed the presence of Ti³⁺, oxygen vacancies and electron interactions with organic compounds on the catalyst surface. In the case of the TNR + NF(0.7) sample, high photocatalytic activity was observed in the H₂-assisted reduction of NO₂ to N₂ at room temperature under visible-light illumination. In contrast, the TNR + NF(1.4) catalyst as well as the heat-treated samples showed no ability to reduce NO₂ under visible light, indicating the presence of deformed Au NFs limiting the LSPR effect. These results emphasized the importance of the choice of synthesis method, as this could strongly influence the photocatalytic activity of the Au NFs.