Herein, we report the synthesis of a novel heterohexanuclear complex (1) of a heteroaromatic cofactor, pyrroloquinolinequinone (PQQ). The crystal structure of 1 was determined to reveal that two PQQ: bridged (RuAgI)-Ag-II units were linked by two [Ag-I(OTf)(2)](-) units (OTf = CF3SO3-). A solvent-bound (RuAgI)-Ag-II heterodinuclear complex (2) was formed from 1 in a coordinating solvent such as acetone to show an intense metal-to-ligand charge-transfer band at 709 nm.