Although luminescent indium(III) based halide perovskites have been widely investigated, the study of emissive indium(III) halide hybrids is limited. Three indium(III) chloride hybrids based on a bpym ligand were synthesized, namely [EPy]2[InCl4(bpym)InCl4]·DMF (1), [EPy]2[InCl4(bpym)InCl4] (2), and [BPy]2[InCl4(bpym)InCl4] (3) (EPy = N-ethylpyridinium; BPy = N-butylpyridinium; bpym = 2,2'-bipyrimidine). They all exhibit a zero-dimensional structure, in which the ligand bpym interconnects two [InCl4]- to form a [InCl4(bpym)InCl4]2- anion that is further charge-compensated by the corresponding pyridinium cations. This is the first time using bpym to coordinate with an In atom. At 298 K, 1 exhibits a weak emission at 600 nm while 2 and 3 exhibit emissions peaking at 500 nm and 540 nm, respectively. Interestingly, the DMF solvent molecule in 1 can be removed by heating, thus resulting in the structural transformation of 1 into 2 together with a photoluminescence (PL) change. Density functional theory (DFT) calculations confirm that halogen-to-ligand charge-transfer (HLCT) occurs in the emission process. To the best of our knowledge, this is the first report on PL of ionic indium(III) halide hybrids incorporating organic ligands.