Polystannanes are a unique class of materials as those inorganic polymers (more precisely organometallic polymers) appear to be hitherto the only characterized polymers with a backbone of covalently bound metal atoms. This review reflects the synthesis, spectroscopic characterization (in particular ¹¹⁹Sn NMR and UV-vis spectroscopy), physical properties and material properties of polystannanes, and their processing into (oriented) films and fiber blends.