Fuel cell and water electrolyzer technology have been intensively investigated in the last decades toward sustainable and renewable energy conversion systems. For improved device performance and service life, nanostructured electrocatalysts on electrode have been extensively developed based on the principle of structure-activity-stability correlation. However, overall device efficiency is seriously hindered by sluggish oxygen electrocatalysis, including oxygen reduction reaction and oxygen evolution reaction. As a result, tremendous efforts have been made to construct the most active surfaces with robust durability. For knowledge-based approaches toward systematic development of highly functional nanostructures, fundamental principles within oxygen electrocatalysis should be uncovered including reaction intermediate, active site structures, and atomic dissolution from surface. However, conventional ex situ characterizations only provide a static picture of electrode surfaces without electrocatalysis. On the other hand, in situ/operando analyses allow us to directly monitor dynamics on electrode under operating conditions. In this review, we will introduce a set of in situ/operando analytical tools and summarize their contribution to fundamental researches on oxygen electrocatalysis. Taking both precious and non-precious electrocatalyst materials as examples, the most impending issues in oxygen electrocatalysis are covered with in situ/operando studies to highlight the power of in situ/operando techniques and encourage further efforts on advanced analytic techniques.