The introduction of a material with two or more different physical and chemical properties into a complicated system to realize multitasks is an emerging trend, but designing and synthesizing bi-/multifunctional materials with well-defined mechanical tasks at the molecular level face great challenges. Herein, coordination polymers (CPs) were designed and synthesized as bifunctional molecular materials combining catalytic activity and triboelectric behavior to construct a self-powered photocatalytic system. By constructing a series of isostructural complexes with different central metal centers (Cd-CP, Mn-CP, and Mn/Cu-CP) and utilizing them as triboelectric layers to engineer CP-based triboelectric nanogenerators (TENGs), the output performance of TENGs was systematically explored and regulated. The electrical characterizations indicated that TENG based on Mn/Cu-CP exhibited the highest output, which attributed to the electron transfer facilitated by CuII ions. The Mn/Cu-CP-TENG presented optimal output and excellent stability could directly power blue lamp beads as a visible light source, which successfully induced a photocatalytic decarboxylative oxygenation reaction with Cd-CP, Mn-CP, and Mn/Cu-CP as catalysts. The results showed that Mn/Cu-CP was a high-efficient and stable photocatalyst to efficiently facilitate the photocatalytic process. This study not only demonstrated that the metal centers in CPs were significant influence the output performance of TENG, but also provided a pathway to highlight bifunctional CPs as triboelectric materials and catalysts.