Antimony based organic–inorganic hybrid compounds (Ph4P)2SbCl5 (Ph4P: tetraphenylphosphonium) and (DTA)2SbCl5 (DTA: dodecyltrimethylammonium) with a zero-dimensional structure were fabricated, and the optical and scintillation characteristics were evaluated. A broadband photoluminescence possibly due to self-trapped exciton (STE) emission appeared at 692 nm for (Ph4P)2SbCl5 and 630 nm for (DTA)2SbCl5 under 370 nm excitation light. The quantum yields were 98 % for (Ph4P)2SbCl5 and 97 % for (DTA)2SbCl5. Under X-ray, the broad emission peak was also detected at 670 nm for (Ph4P)2SbCl5 and at 615 nm for (DTA)2SbCl5. Furthermore, scintillation decay time constants were 4.9 μs for (Ph4P)2SbCl5 and 5.0 μs for (DTA)2SbCl5. Moreover, the scintillation light yield of (Ph4P)2SbCl5 was estimated to be about 12,000 photons/MeV, whereas the light of (DTA)2SbCl5 could not be determined. In addition, afterglow levels were 56 ppm for (Ph4P)2SbCl5 and 130 ppm for (DTA)2SbCl5.