Herein, an interesting light-induced self-assembly behavior from non-photoresponsive gold nanoparticles (Au NPs) was reported. Specifically, a pH-responsive amphiphile SPBwas developed that contained a particular phenylboronic acid moiety and showed excellent surface activity at the neutral and basic conditions, thereby stabilizing Au NPs well. Accordingly, the SPB-functionalized Au NPs showed strong pH dependence that there presented the pH induced reversible self-assembly behavior. Furthermore, the introduction of a small amount of commercially available photoacid generator named diphenyliodonium nitrate (DIN) into the system could endow it with apparent light-switchable self assembly behavior. The pH- and light-induced self-assembly behaviors of SPB-functionalized Au NPs in the absence and presence of DIN, respectively, were systematically studied by various techniques including UV vis spectrum, transmission electron microscope, nuclear magnetic resonance, and Fourier transform infrared spectroscopy, which evidently confirmed that the stimuli-responsive self-assembly was controlled by the hydrogen-bonding interactions between phenylboronic acid moieties. Attributing to the light-induced obvious color change from bright-red to deep purple, the system was applied in particle imprinting successfully.