A series of cross-linked piperidinium-based anion-exchange membranes (AEMs) with an aliphatic main chain was prepared by UV-initiated polymerization of 1-methyl-1-(4-vinylbenzyl)piperidinium chloride ([MVBPip][Cl]). The chemical structures of ([MVBPip][Cl]) and piperidinium-based membranes were studied by nuclear magnetic resonance (NMR) and IR spectroscopy, respectively. The piperidinium cation showed excellent alkaline stability, demonstrated by H-1 NMR spectroscopy. The water uptake and conductivity of the piperidinium-based AEMs were enhanced by an increase in [MVBPip] [Cl] content. A hydrophilic/hydrophobic microphase-separated structure was clearly detectable in the piperidinium-based AEMs. The transparent and mechanically robust piperidinium-based AEMs exhibited excellent chemical stability in 2 M KOH solution with the conductivity reaching 57.4 mS cm(-1)(80 degrees C). The maximum power density of the single cell fabricated with piperidinium-based AEMs achieved 108.8 mW cm(-2). These results indicate that the cross-linked piperidinium-based AEMs with an aliphatic main chain are promising materials for application in fuel cells.