A light‐harvesting system based on the coordination of benzimidazole derivatives (G) and Zn2+ was successfully prepared. Compared with G, the G−Zn2+ assembly exhibited a noticeably enhanced fluorescence emission band. As such, it was employed as the donor in fabricating the artificial concentrating light‐harvesting systems, with acridine yellow and acridine orange employed as acceptors. In these two systems (G−Zn2+/acridine yellow and G−Zn2+/acridine orange), the occurrence of an energy‐transfer process was confirmed from the G−Zn2+ assembly to acridine yellow and acridine orange, separately. The findings of this study will facilitate the development of artificial light‐harvesting systems.