A new organic-inorganic complex, bis(4-amine pyridinium) aquapentachloroindoidate(III) (C5H7N2)2[InCl5(H2O)], was synthesized and characterized by single crystal and powder X-ray diffraction, Hirshfeld surface, vibrational spectra, thermal analyses (TGA and DTA) and NMR 13C. Compound crystallizes in triclinic P-1 space group (a = 6.8852(3) Å, b = 11.6914(5) Å, c = 11.9603(6) Å, α = 108.812(4)°, β = 102.028(4)°, γ = 92.835(3)°, Z = 2) with alternation of organic and inorganic layers along the a-axis. The crystal packing was governed by the NH⋯Cl and OH⋯Cl hydrogen bonding interaction between the 4-amine pyridinium cations and the octahedral [InCl5(H2O)] anions, and π-π stacking interactions in which they may be effective in the stabilization of the crystal structure. The optical and photoluminescence properties of the compound were investigated in the solid-state at room temperature.