We present a facile, high-yield synthetic route to linear poly(dibutylstannane) of relatively high molecular weight (M_w = 20 × 10³ g mol⁻¹) through dehydropolymerization of dibutylstannane with the catalyst [RhCl(PPh₃)₃]. Unlike previously synthesized polystannanes, the present materials were entirely free of cyclic oligomers. A reversible phase transition was observed at a temperature of ∼1 °C, which was found to be associated with a marked change in crystalline order. The material appeared to be in a liquid-crystalline-like state at room temperature and could be readily oriented by simple shearing processes, which resulted in highly ordered films.