Transition metal based materials containing Fe have drawn great attention as oxygen evolution reaction (OER) catalysts. The nature of the electrocatalytic active species remains under debate due to the ambiguous physicochemical properties of the catalyst materials, such as the oxidation states and crystal structures. Here, in order to address this issue, transition metal Prussian blue analogues (TM-PBA, Na(TM)(Fe)(CN)₆, TM = V, Fe, Co, and Ni) with an isomorphous structure are investigated for OER catalysis. Our combined experimental measurements and density functional theory (DFT) calculations reveal that TM-PBAs exhibit volcano-like OER activity with Ni-PBA located near the top of the volcano. Such a volcano-like activity profile can be attributed to the distinctive binding energy difference between *O and *OH on different TM-PBAs surfaces. This work demonstrates that TM-PBAs can be used as platform materials for understanding structure-property-activity relationships in OER catalysts.

含铁的过渡金属基材料作为氧气析出反应（OER）催化剂备受关注。由于催化剂材料的物理化学性质不明确，例如氧化态和晶体结构，电催化活性物质的性质仍在争论中。在这里，为了解决这个问题，过渡金属普鲁士蓝类似物（TM-PBA，NaTM（Fe）（CN）₆（TM = V，Fe，Co和Ni）具有同晶结构的OER催化剂进行了研究。我们结合的实验测量结果和密度泛函理论（DFT）计算表明，TM-PBA表现出类似于火山的OER活性，而Ni-PBA位于火山顶部附近。这种类似火山的活动曲线可归因于不同TM-PBA表面上* O和* OH之间的独特结合能差异。这项工作表明TM-PBA可用作理解OER催化剂中结构-性质-活性关系的平台材料。