<p>Organic–inorganic hybrid halide perovskites have attracted attention in optoelectronics and photovoltaics. However, the Pb-content in the crystal structure and instability issues have raised questions about the industrialization of these materials. Bi and Sb are widely considered as an alternative on the B-site due to their isoelectronic configuration with the Pb divalent cation. Herein, we report four novel Pb-free azetidinium metal halides and present their fundamental material properties: [(CH₂)₃NH₂]₂AgBiBr₆, [(CH₂)₃NH₂]₃Bi₂I₉, [(CH₂)₃NH₂]₃Bi₂Br₉, and [(CH₂)₃NH₂]₃Bi₂Cl₉. Our materials have a low-dimensional perovskite-like structure from 0 to 2D, where the replacement on the B-site is based on Ag⁺/Bi³⁺ and Bi³⁺.</p> Graphical Abstract <p>As a potential light absorber, four different azetidinium metal halides were successfully synthesized <i>via</i> evaporation. The polycrystalline powders and thin films of the azetidinium metal halides present low dimensionalities from 0 to 2D.</p> <p></p>