AbstractThe self‐condensation of the ferrocenyl Mannich base, N,N‐dimethylaminomethylferrocene, in the presence of a ZnCl2HCl catalyst system in the melt phase leads to soluble polymers containing ferrocenylene units interlinked by methylene groups. The crude condensation products exhibit number‐average molecular weights in the range 4000–8000. Elemental and infrared spectroscopic analyses as well as viscometric data show the structure to be essentially identical with that of the polymer derived from hydroxymethylferrocene described in an earlier communication. The optimum molar ratio of the reactants (Mannich base, ZnCl2, and HCl) is 2:1:2. Dimethylammonium tetrachlorozincate has been isolated as by‐product, and an intermediary complex composed of Mannich base, ZnCl2, and HCl in the same 2:1:2 ratio has been intercepted during the polycondensation. Some mechanistic inferences are discussed.