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Direct probing solid-liquid interface is the first step to truly understand an electrochemical system,where the electrochemical interface plays a crucial role.However,it has been a challenge to look through the dense liquid or solid layer and to monitor the thin electrochemical interface while the electrochemical reactions are happening.Many groups have tried to use different in-situ techniques to address this challenge.Particularly,several significant advances have been made recently to probe the electrochemical interface under in situ and operando conditions using synchrotron radiation based characterization tools.Ambient pressure X-ray photoelectron spectroscopy(APXPS)is one of them [1].In this talk,I will give a brief history how our group developed APXPS techniques using soft X-ray and tender X-ray to probe the electrochemical interface directly [2] and show several in-situ studies [3,4] on electrolyte/electrode interfaces.