The alkaline stability of organic cations tethered to anion-exchange membranes (AEMs) is essential for the long-term performance of alkaline membrane fuel cells and electrolyzers. Here, we have prepared and studied the thermal and alkaline stability of a series of polyelectrolytes functionalized with N-spirocyclic quaternary ammonium (QA) cations. N,N-Diallylazacycloalkane quaternary salts were readily synthesized by diallylation of pyrrolidine, piperidine, azepane, and morpholine. These monomers were employed in radical initiated cyclo-polymerizations to obtain the target poly(N,Ndiallylazacycloalkane)s. H-1 NMR spectroscopy revealed that the stability of the polyelectrolytes in 2 M KOD/D2O solutions critically depended on the ring size and the absence of additional heteroatoms in the ring. Thus, poly(N,N-diallylpiperidinium) showed the highest alkaline stability, with only minor signs of degradation at 120 degrees C after 14 days, while the polyelectrolytes based on the morpholine and azepane rings clearly degraded via both Hofmann elimination and ring-opening substitution already at 90 degrees C. Cross-linked water nonsoluble AEMs were prepared by copolymerizing N,N-diallylpiperidinium chloride with methylbenzyldiallylammonium groups tethered to poly(phenylene oxide). These transparent and mechanically robust AEMs reached high OH- conductivities, above 0.1 S cm(-1) at 80 degrees C. The present work demonstrates the high alkaline stability of suitably configured N-spirocyclic QA cations, which will open up new prospects for readily accessible high performance polyelectrolytes and membranes.