The production of the industrially significant radionuclide polonium-210 from the neutron irradiation of bismuth metal and the subsequent beta decay of bismuth-210 is highly inefficient due to the small neutron capture cross section of bismuth-209. In this paper, we report a previously undescribed self-sustaining nuclear chain reaction involving self-propagating neutron multiplication in bismuth salts that allow for rapid and cost-effective production of polonium-210. The reaction proceeds in a cycle of three alternating elementary steps – the capture of neutrons by bismuth-209 and the subsequent formation of polonium-210, the emission of high-energy alpha particles by polonium-210, and the production of more neutrons from (α,n) and (n,2n) reactions on light element and bismuth-209 nuclei respectively. Furthermore, the high hydrogen density of the compound also confers it intrinsic neutron moderation properties, increasing the neutron capture cross section of bismuth-209 at thermal neutron energies. The chain reaction was proven to have successfully occurred by irradiating a sample of the bismuth salt with a 80 µCi neutron source and monitoring the activity levels of the reaction. It was found that the activity of the reaction increased exponentially after an initial stable period following a derived formula for polonium production trends for the reaction, thus validating the occurrence of the reaction. Furthermore, alpha spectroscopy confirmed that polonium-210 had been produced by characterising the 5.30 MeV alpha emission peak of the reaction in addition to using beta spectroscopy to identify the parent nuclide bismuth-210, further proving that the reaction was successful. Hence, this paper reports the successful initiation and characterisation of a novel nuclear chain reaction, and its potential applications offered by a method of rapidly producing large quantities of polonium-210.