The new interesting organic-inorganic hybrid compound with the title (C9H12N4)2[BiBr6].Cl.4H2O was synthesized and grown using the hydrothermal method. Single-crystal X-ray diffraction analysis revealed that the new supramolecular compound adopts the non-centrosymmetric space group Pmn21 in the orthorhombic system. The unit cell parameters are as follows: a = 20.1193 (2) Å, b = 10.7704 (10) Å, c = 7.8356 (10). The crystalline structure of the new compound was solved using Direct methods and refined using the least squares method to achieve final values of R1 = 0.0239 and wR2= 0.0628.The purpose of conducting Hirshfeld surface analysis was to investigate the interactions between molecules and the 2D fingerprint plots associated with them, confirming the existence of hydrogen bond interactions and indicating that the Br⋯H/H⋯Br interaction is the most dominant, accounting for 50 % of the total interactions. FTIR spectroscopy and Raman scattering were used to identify the functional and molecular groups present in the crystal by analyzing their vibration modes. The energy gap value for the titled compound was calculated and confirmed by the DOS spectrum. Finally, the thermal behavior of the compound was characterized by thermogravimetry (TGA) analysis.