Abstract: Synthesizing atomically precise Ag nanoclusters (NCs), which is essential for the general development of NCs, is quite challenging. In this study, we report the synthesis of high-purity atomically precise Ag NCs via a kinetically controlled strategy. The Ag NCs were prepared using a mild reducing agent via a one-pot method. The as-prepared Ag NCs were confirmed to be Ag₄₉(D-pen)₂₄ (D-pen: D-penicillamine) on the basis of their matrix-assisted laser desorption ionization time-of-flight mass spectrometric and thermogravimetric characteristics. The interfacial structures of the Ag NCs were illustrated by proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy. The Ag NCs were supported on activated carbon (AC) to form Ag NCs/AC, which displayed excellent activity for the catalytic reduction of 4-nitrophenol with a kinetic reaction rate constant k of 0.21 min⁻¹. Such a high k value indicates that the composite could outperform several previously reported catalysts. Moreover, the catalytic activity of Ag NCs/AC remained nearly constant after six times of recycle, which suggests its excellent stability.