Tow novel hybrid compounds, (C5NH6)6Bi4Br18 and [C(NH2)3]3BiI6 were synthesized at room temperature by slow evaporation. The crystal packing is ensured by hydrogen bonds. The phase transition of (C5NH6)6Bi4Br18 and [C(NH2)3]3BiI6 were studied using the DSC experiments. These materials were also investigated by elemental analysis and XRPD.