Exploiting cost-effective trifunctional electrocatalysts toward oxygen evolution reaction, hydrogen evolution reaction and oxygen reduction reaction is important for sustainable energy conversion and storage devices yet challenging. Here, we report a single-phase trifunctional electrocatalyst Sr2CoRuO6-δ with well-defined super-exchange double perovskite structure, which can efficiently catalyze oxygen evolution, hydrogen evolution and oxygen reduction under alkaline conditions. As an air electrode, Sr2CoRuO6-δ delivers high peak power density of 216 mW cm−2, high specific capacity of 748 mAh g−1 and long lifespan up to 1000 h for liquid rechargeable zinc-air batteries, as well as broad temperature and deformation adaptability for solid-state flexible zinc-air batteries. Furthermore, an anion exchange membrane water electrolyzer employing Sr2CoRuO6-δ as both cathode and anode requires a cell voltage of 1.90 V at the current density of 1 A cm−2 and shows a stable and rapid response when coupled with fluctuating solar electricity. Combining complementary in-situ and microscopic techniques, spatiotemporal surface reconstruction behavior of Sr2CoRuO6-δ under varied reactions is comprehensively investigated and true active components are identified.