Atomically precise copper clusters are an emerging class of functional materials with considerable promise in photocatalysis and luminescence. However, integrating strong emission and high catalytic efficiency within a single robust structure remains a significant challenge. Herein, we report a straightforward synthetic strategy to construct a trinuclear copper cluster, Cu3(dppm)3(PE)2 (Cu3), co-protected by bis(diphenylphosphino)methane (dppm) and 4-ethynylbenzoic acid (PE). The resulting cluster exhibits pronounced aggregation-induced emission (AIE) behavior together with excellent photocatalytic activity, establishing it as a dual-functional copper cluster. Under environmentally benign conditions using air as the oxidant, the Cu3 cluster efficiently catalyzes the oxidative coupling of benzylamines, affording up to 99% conversion rate within 3 hours. Notably, its catalytic performance significantly surpasses that of control systems employing copper salts or PE alone, highlighting the structural advantage of the atomically precise cluster framework. This work provides new insights into the rational design of multifunctional copper-based clusters.