Despite a well-established and growing body of work on nickel(0) precatalysts, the potential of nickel(0) complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, and evaluated the catalytic activity of (Ni(0)(DQ)dtbbpy), a bifunctional, red-light-sensitive, and air-stable nickel(0) complex. Owing to its unique photophysical properties, it effectively catalyzed the etherification and amination of aryl bromides under 620-630 nm light irradiation, functioning as both a photocatalyst and an active metal catalyst. Mechanistic studies and density functional theory (DFT) calculations further confirmed the exceptional absorption properties of Ni(0)(DQ)dtbbpy in the red-light region, as well as the electron transfer process triggered by red-light irradiation.