Low-dimensional metal halide hybrid perovskites have received extensive attention owing to their versatile structures and optoelectronic properties. Here, we report a new low-dimensional lead-free hybrid, [C₆H₅(CH₂)₂CH(NH₃)CH₃]₂BiCl₅ (MPA₂-BiCl₅). Experiments reveal that MPA-BiCl₅ consists of a binuclear BiCl₆ octahedron and four disordered MPA cations. Moreover, the indirect band gap is determined to be 3.20 eV and is affected by inorganic anions.