Developing for highly active and stable electrocatalysts for oxygen evolution reaction (OER) is of significant importance for some renewable energy conversion and storage systems. While, the prerequisite for further optimizing the activity of electrocatalysts is whether their original composition has potential for development. Herein, we firstly managed to combine theoretical and experimental efforts to establish Ru0.4Sn0.3Ce0.3O2 (RSCO) as a promising electrocatalyst for acidic OER. The X-ray absorption and density functional theory studies reveal that the local coordination environment and electronic structure of Ru sites in RSCO is optimized by the oxygen atom bridged Sn and Ce at heterogeneous interfaces, thereby resulting in a low energy barrier. In addition, the electrochemical results indicate that the activity and stability of RSCO obviously surpasses that of the RuO2 prepared by same method as RSCO. Most encouragingly, the OER activity of RSCO can be substantially enhanced only by optimizing the calcination temperature, meaning the possibility of further improvement the intrinsic activity of such oxygen atom bridged Ru based complex by proper surface or interfacial engineering.