A gallium-bridged polyferrocene was prepared via spontaneous ring-opening polymerization of a galla[1]ferrocenophane. This organometallic polymer is thermally robust and can be purified and handled under ambient conditions, making it an ideal candidate flor incorporation into polymer based materials offering all alternative to existing poly ferrocenes. The tBu group pointing toward the polymer backbone serves as a very sensitive NMR probe of the polymer stereochemistry.