Abstract Aiming to design a catalyst for stable electrooxidation of water at low pH, the present work explores the properties and structural features of electrodeposited composite oxides based on Bi and Co, which were anticipated to provide stability and catalytical activity, respectively. Materials deposited as very thin ( ca 50 nm) films on F‐doped SnO 2 (FTO) substrate do not initially exhibit high activity in 0.1 M H 2 SO 4 , but are activated during operation through the electrooxidatively‐induced enrichment of the catalytic surface with Co and Sn oxides. The latter originate from the FTO support and are identified as an important component of the catalyst through control experiments with a Sn‐free substrate and with Sn 2+ intentionally added at the electrodeposition stage. A distinctive feature of the Co−Bi−Sn‐based electrocatalyst is the slow but persistent improvement in the activity during operation in 0.1 M H 2 SO 4 at both ambient and elevated (60 °C) temperatures, which contrasts with the continuously degrading behaviour of state‐of‐the‐art oxygen evolution catalysts at low pH. This is demonstrated by 9‐day‐long galvanostatic tests at 10 mA cm −2 , during which the Co−Bi−Sn‐based thin film catalyst shows no degradation and sustains stable water oxidation at ca 1.9 V vs . reversible hydrogen electrode. The effects of tin leaching from the support detected herein might have implications to other acidic water oxidation catalysts supported on high‐surface area doped SnO 2 materials.