We report a one-pot, three-component synthesis of dibenzophosphole under mild conditions, facilitated by a copper–silver bimetallic system. This method employs readily available cyclic diaryliodonium salts as arylation reagents and sodium phosphaethynolate (NaOCP) as a phosphorus source, eliminating the need for lithium reagents and energy-intensive chlorophosphines. The resulting dibenzophosphole derivatives exhibit strong fluorescence, highlighting their potential as fluorescent materials.