© The Author(s) 2019. We report a new additive, monobasic potassium arsenate (KH2AsO4), for improving the thermal stability of VFB catholytes. Using our standard accelerated testing methodology at 30¿70°C, we showed that the effect increases continuously with increasing concentration of arsenate over the range investigated (0 ¿ 0.10 mol dm¿3). In comparison to similar experiments with phosphate (H3PO4), the magnitude of the effect was greater for arsenate. A combination of arsenate and phosphate was also effective. Based on these results, we speculate that other Group-V elements in the +5 oxidation state may also stabilize VFB catholytes.