Gold is designated as the noblest metal because of its chemical inertness. It is known to dissolve in cyanide solutions in the presence of air or H2O2 or in halogen-containing solutions, aqua regia being the most famous example. Herein, we report a unique thiol, especially 4-pyridinethiol (4-PS), assisted dissolution of Au in alcohol solutions. Although dissolution was found to be very selective for pyridinethiols, such a phenomenon is astonishing since thiols are commonly used as etch resists for Au and even 4-PS is extensively used as a surface modifier for Au. To gain further understanding of the dissolution process, the influence of the reaction conditions was extensively studied. On the basis of the obtained results, a mechanism for the dissolution reaction is proposed. Fascinatingly, by tuning of the reaction conditions, this phenomenon can be applied in selective preparation of self-supporting nanometer-thick Au foils.