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In this work, a lead-free organic-inorganic hybrid crystal with dual functions of green-emission and bactericidal activity, benzyl triethylaminium tetrachloromanganate(II) ([BzTEA]2[MnCl4]), was synthesized by the slow evaporation solution growth technology and characterized by single-crystal and power X-ray diffraction, IR spectrum, Scanning Electron microscopy, and PL spectrum. The compound crystallized in the monoclinic space group P21/c. The thermal study revealed that the material showed good thermal stability and can be used for applications below 222.1 °C. The material had excellent optical properties as it fluoresced green under 350 nm UV light. The compound exhibited favorable bactericidal activity against Staphylococcus aureus and Escherichia coli. An inorganic-organic hybrid salt [BzTEA]2[MnCl4] was synthesized and characterized. The salt shows green fluorescence emission at 534 nm in a solid state at room temperature. The salt exhibited favorable thermal stability and could be used in applications below 222.1 °C. The salt had an optical band gap of 1.66 eV and was a typical semiconductor material with good optical properties. The as-synthesized salt exhibits good antibacterial activities against S. aureus and E. coli. [ABSTRACT FROM AUTHOR]