In this work, we synthesize a series of hierarchically organized gold nanoparticles (Au HOPs-X) with peroxidase (POD)-like catalytic activity by the in situ reduction of Au−thiolate hierarchically organized particles (Au HOPs). The initial Au HOPs show little PODlike catalytic activity. However, after the reduction of the particles, the Au HOPs-X showed enhanced POD-like catalytic activity, where X represents the reduction degree of Au HOPs. The reasons are as follows:(1) the Au−thiolate complexes on the surface of the Au HOPs-X were reduced into Au nanoparticles, and the active Au 0 content increases with the increase of the reduction degree; (2) the specific surface area of Au HOPs-X becomes larger. Based on this, the Au HOPs-10 with the highest catalytic activity were combined with glucose oxidase to obtain a standard curve as a function of glucose concentrations. The color of the solutions was captured by mobile phone photos to determine their saturation, and the rapid detection of glucose was achieved through the standard curve of glucose concentration and saturation determined in this study.