The development of cationic polymers for anion-exchange membranes (AEMs) with high alkaline stability and conductivity is a considerable challenge in materials chemistry. In response, we here present the synthesis and properties of N-spirocyclic quaternary ammonium ionenes (spiro-ionenes) containing 5- and 6-membered rings fused by central nitrogen cations. High molecular weight and film-forming Spiro-ionenes are successfully synthesized in cyclo-polycondensations of tetrakis(bromomethyl)benzene and dipiperidines under mild conditions. These polyelectrolytes show excellent thermal and alkaline stability with no degradation detected by NMR spectroscopy after more than 1800 h in 1 M KOD/D2O at 80 degrees C. Even at 120 degrees C, the spiro-ionenes display reasonable alkaline stability. Transparent and mechanically robust AEMs based on ionically cross-linked blends of spiro-ionene and polybenzimidazole reach OH- conductivities up to 0.12 S cm(-1) at 90 degrees C. The current findings demonstrate that spiro-ionenes constitute a new class of alkali-stable anion-exchange polymers and membranes.