Pursuits of new types of Pb-free heterometallic halides adequate for photovoltaic applications are still urgent but challenging. In this study, by using in situ-produced [(Me)2-(DABCO)]2+ (DABCO = 1,4-diazabicyclo[2.2.2]octane; Me = methyl) cations as structure-directing agents, we successfully constructed a non-perovskite copper iodobismuthate hybrid, namely [(Me)2-(DABCO)]2Cu2Bi2I12 (1), which features discrete [Cu2Bi2I12]4- anionic moieties formed by the building units of [CuI4] tetrahedra and [BiI6] octahedra. UV-Vis diffuse reflectance analyses showed that compound 1 possesses semiconductive behaviors with a narrow optical bandgap of 1.80 eV. More importantly, it exhibits excellent photoelectric switching abilities, and its photocurrent density (2.30 μA cm-2) far exceeds those of some high-performance halide-based counterparts. Different from many heterometallic analogues, noteworthily, it also has dispersive band structure and strong electronic coupling near the Fermi level, resulting in a material with small effective masses that may be responsible for the good photoelectricity. This study may offer new guidance for the design and synthesis of eco-friendly heterometallic halides with unique structures and desirable properties.