The polymerization reactions of styrene oxide (SO) at different temperatures for different time intervals were performed by four different tin catalysts, tin(IV) perfluorooctanoate (PFO-Sn), tin(IV) methacrylate (MAc-Sn), tin(II) chloride (SnCl2), and SnCl2/hexamethyldisilazane. Tin(IV) perfluorooctanoate and methacrylate compounds have been prepared from perfluorooctanoic acid, methacrylic acid, and tin tert-butoxide in tert-butanol. The Sn-PFO and Sn-MAc compounds were characterized by H-1, C-13 NMR, FTIR, and elemental analysis. These four compounds were tested as catalysts in polymerization of SO and were effective. Polystyrene oxide (PSO) was characterized by H-1, C-13 NMR, and gel permeation chromatography. High molecular weight of PSO (~138,000Da) was recorded for the first time by this study.