Two-dimensional (2D) gold nanoplates (AuNPLs) have shown potential in catalysis, photonics, electronics, sensing, and biomedicine fields due to their high aspect ratio, fascinating surface chemistry, and quantum-size effect. Therefore, the synthesis of substrate-free, size-controlled single-crystal gold (Au) nanoplates is highly desirable for the development of catalysis and optical near-field enhancement applications. EDTA and hydroxide anions were used in this study to stimulate the formation of microscale single-crystal gold nanoplates under hydrothermal conditions. The reaction temperature, amount of EDTA, and hydroxyl anions all have a significant effect on the morphologies and size distributions of the gold nanoplates. The gold nanoplates had an average side length of between 3 and 11 μm. The application of the microscale single-crystal gold nanoplates as a nanocatalyst proved their excellent catalytic activity and recyclability for the catalysis of 4-nitrophenol to 4-aminophenol, implying that the large-size gold nanoplates were promising in heterogeneous catalysis applications.