Organic-inorganic hybrid materials with perovskite structure have recently attracted tremendous interest due to their structural tunability and rich functional properties, such as phase transition and photoelectric properties. Within this context, two discrete tin-based organic-inorganic hybrid compounds [(FMBA)2SnCl6] (1) and [(FMBA)2SnBr6] (2) were prepared by the reaction of 3-fluoro-N-methylbenzylamine (FMBA) with SnX4 (X = Cl, Br) in the corresponding concentrated halogen acids HX. Differential scanning calorimetry (DSC) and dielectric measurements showed that both compounds underwent reversible phase transition and dielectric anomaly at a phase transition point above 400 K. Crystal structure analyses revealed that the phase transition mainly originated from the order and disorder of a fluorine-substituted organic amine structure at low and high temperatures. Meanwhile, both compounds showed a semiconducting property with optical bandgaps of 4.24 eV for 1 and 2.58 eV for 2. This finding of two Sn(iv)-based metal halides with prominent phase transition and semiconducting behaviors will expand an executable pathway for designing multifunctional perovskite-type switchable materials.