Inspired by the successful utilization of aziniums as anolytes in redox-flow batteries, we have designed and prepared a systematically extended series of (di)azinium compounds based on pyrazine, bipyridine, 1,5-naphthyridine, 3,8-phenanthroline, (E)-4,4'-diazastilbene and 1,2-bis(pyridin-4-yl)acetylene. It has been revealed that the fundamental electrochemical properties are affected mostly by the water-solubility and chemical stability of the particular redox forms. Based on the systematically evolved azinium structure and gathered electrochemical data, structure-property relationships were thoroughly elucidated. Further investigation on flow battery cells identified that the known 4,4'-bipyridinium decorated with two peripheral N-propyl-3-sulfonato pendants allows utilizing both redox steps with good cycling stability, while the naphthyridine scaffold turned out to be a new and promising scaffold for redox-flow batteries.