Low-dimensional organic–inorganic hybrid metal halides, with broadband luminescence, have attracted much attention for optoelectronic applications due to their rich in structural diversity and solution processibility. However, it is still unclear about how the solvent molecules influence the optoelectronic properties of the solution processed low-dimensional metal halides. Here, we prepared five different antimony-based crystal structures, [SbCl₆]^3- as the metal halide octahedron and 4, 4-difluoropiperidine (DFPD⁺) as organic cation, by using different solvents: hydrochloric acid (HCl) aqueous solution and four organic solvents (dimethylformamide (DMF), methanol (MeOH), acetonitrile (ACN) and dimethylacetamide (DMAC)). We revealed the relation between their crystal structures and optical properties, and we found the participation of organic molecules in the crystal structure causes significant lattice distortions, which is beneficial for achieving self-trapped exciton (STE) emission. Among them, (DFPD)₆SbCl₉·2DMAC exhibits a remarkable photoluminescence (PL) quantum yield of approximately 90 %. The STE dynamics in (DFPD)₆SbCl₉·2DMAC were characterized by femtosecond transient absorption and time-resolved PL spectroscopies. Simultaneously, this study also provides new directions for expanding the application of low-dimensional luminescent metal halides: in addition to UV-LEDs, efficient and rapid detection of methanol or acetonitrile can be achieved using the raw materials, while also realizing the potential application of multi-level optical anti-counterfeiting.