Precisely tuning the structure of nanomaterials, especially in a two-way style, is challenging but of great importance for regulating properties and for practical applications. The structural transformation from nonfcc to fcc (face center cubic) in gold nanoclusters has been recently reported; however, the reverse process, that is, the structural transformation from fcc to nonfcc, not to mention the two-way structural transformation between fcc and nonfcc, remains unknown. We developed a novel synthesis method, successfully fulfilled the two-way structure transformation, and studied the stability of gold nanoclusters with different structures. Additionally, a novel gold nanocluster was synthesized and structurally resolved by single-crystal X-ray crystallography. This work has important implications for structure and property tuning of gold nanoclusters and might open up some new potential applications for gold nanoclusters.