Noble metal nanoclusters have emerged as a fascinating area of widespread interest in nanomaterials. Herein, we report the synthesis of the PEI-templated gold nanoclusters (PEI-AuNCs) as an efficient carrier for gene delivery. The PEI-AuNCs integrate the advantages of PEI and AuNCs: the presence of AuNCs can effectively decrease the cytotoxicity of PEI, making it possible to apply them in biological systems, while the cationic polymer layer PEI with positive charges is essential for enhanced gene transfection efficiency. In addition, with excellent photoluminescent properties, the AuNCs also endow our system with the versatility of fluorescent imaging, indicating a great potential as an ideal fluorescent probe to track the transfection behavior. Our studies provide strong evidence that the PEI-AuNCs can be utilized as efficient gene delivery agents.