Hybrid organic-inorganic metal halide materials with zero-dimensional (0D) structures have emerged as a captivating field of research due to their distinctive electronic properties and remarkable broadband emission characteristics. In this study, we successfully synthesized a novel hybrid cadmium iodide compound, (BZA)2CdI4.H2O (BZA+: benzylammonium), in the form of single crystals employing the solvent-evaporation method. The room temperature single-crystal X-ray diffraction analysis revealed that (BZA)2CdI4.H2O possesses a typical 0D crystal structure, where (CdI4)2− anions are spatially isolated and surrounded by (BZA)+ cations and H2O molecules. The crystal packing is intricately governed by various non-covalent intermolecular interactions, including π–π stacking interactions, NH…I, NH…O, and OH…I hydrogen bonds, quantified through Hirshfeld surface analysis. Thermal analysis further demonstrated that the removal of water molecules in the crystal lattice yields a dehydrated phase of (BZA)2(CdI4). Upon 330 nm irradiation, the title compound displayed a broad bluish-white light emission, featuring a primary band at 430 nm and a secondary band at 500 nm. Based on photoluminescence spectra measurements and density functional theory (DFT) calculations, the dual-band emission is assigned to the emission of (BZA)+ organic cations and to excitons confined in the [CdI4]2– isolated inorganic tetrahedron, respectively. Interestingly, the presence of isolated molecular units in the 0-D structure results in strongly localized charges and bluish-white light emission with Commission International de l'Eclairage (CIE) colour coordinates (0.23, 0.28). These results confirm the promise of 0D metal-halide hybrids with dual-band emission as luminescent materials for solid-state lighting.