Two perfluorinated potentially polymerizable dichlorostannane monomers, R2SnCl2, [R = (p-CF3C6H4), ((3,5-CF3)2C6H3)] have been prepared in good yield by the comproportionation reactions of the corresponding tetrarylstannanes (1, 2) and tin tetrachloride. The chlorinated monomers 5 and 6 were characterized by X-ray crystallography, 1H, 13C, and 119Sn NMR spectroscopy. The Wurtz coupling behaviour of these dichloromonomers with Na metal in the presence of 15-Crown-5 was also investigated and moderate to very high molecular weight polystannanes 8 and 9 where detected by GPC (Mw = 1.1–1.5 × 105 Da). The introduction of perfluorinated, strongly electron-withdrawing substituents on the phenyl rings of the resulting polystannanes causes a considerable blue-shift (>50 nm) of the σ–σ* λmax transition relative to that of polydiphenylstannane. The perfluorinated groups were designed to impart improved moisture stability relative to non-fluorinated analogues. The new polymers 8 and 9 were found to be extremely light sensitive and readily degraded to oligomeric species upon exposure to ambient light.