Zero-dimensional (0D) metal halides with solid-state luminescence switching (SSLS) have attracted attention as sensors and luminescent anticounterfeiting. Herein, selective solvent molecule response and accordingly luminescence switching were discovered in 0D EtPPh32SbCl5 (1, EtPPh3 = ethyltriphenylphosphonium). More than a dozen kinds of solvent molecules have been tested to find out the selection rule for molecule absorption in 1, which is demonstrated to be the size effect of guest molecules. Confirmed by crystal structural analysis, only the solvents with molecular volume less than 22.3 Å3 could be accommodated in 1 leading to the solvatochromic photoluminescence (PL). The mechanism of solvatochromic PL was also deeply studied, which was found to be closely related to the supramolecular interactions between solvent molecules and the host material. Different functional groups of the solvent molecule can affect its strength of hydrogen bonding with SbCl52–, which is crucial for the distortion level of SbCl52– unit and thus results in not only distinct solvatochromic PL but also distinct thermochromic PL. In addition, they all show typical self-trapped exciton triplet emissions. The additional supramolecular interactions from guest molecules can enhance the photoluminescence quantum yield to be as high as 95%.