Two new hybrid chloroantimonates, namely, [Prmim]₃SbCl₆ (1, Prmim = 1-propyl-3-methylimi- dazolium) and [Hmim]₃SbCl₆ (2, Hmim = 1-hexyl-3-methylimidazolium), were synthesized in ionic liquids (ILs) with the yields of 97% and 72%, respectively. Single-crystal X-ray diffraction (SCXRD) study reveals that 1 crystallizes in monoclinic, space group Pn with a = 15.2988(12), b = 13.6388(10), c = 15.6761(13) Å, β = 98.677(7)°, V = 3233.5(4) ų, Z = 4, D_c = 1.459 g·cm^-3, F(000) = 1440, μ = 1.370 mm^-1, R = 0.0589 and wR = 0.1366 (I > 2σ(I)); 2 crystallizes in the hexagonal space group of P6₃ with a = 27.7471(6), b = 27.7471(6), c = 8.9811(2) Å, V = 5988.2(3) ų, Z = 6, D_c = 1.391 g·cm^-3, F(000) = 2592, μ = 1.121 mm^-1, R = 0.0420 and wR = 0.0726 (I > 2σ(I)). The photophysical properties of the title compounds were studied by solid-state optical absorption, photoluminescent excitation/emission (PLE/PL), PL decay spectra and photoluminescent quantum yield (PLQY). 1 and 2 exhibit PL peaks at 627 and 607 nm, Stokes shifts of 257 and 242 nm, and PLQY of 32.5% and 49.2%, respectively. The distinct photo physical characteristics of 1 and 2 are highly related to the distortion extent of the [SbCl₆]^3- unit.