The increasing demands of energy storage require the significant improvement of current Li‐ion battery electrode materials and the development of advanced electrode materials. Thus, it is necessary to gain an in‐depth understanding of the reaction processes, degradation mechanism, and thermal decomposition mechanisms under realistic operation conditions. This understanding can be obtained by in situ/operando characterization techniques, which provide information on the structure evolution, redox mechanism, solid‐electrolyte interphase (SEI) formation, side reactions, and Li‐ion transport properties under operating conditions. Here, the recent developments in the in situ/operando techniques employed for the investigation of the structural stability, dynamic properties, chemical environment changes, and morphological evolution are described and summarized. The experimental approaches reviewed here include X‐ray, electron, neutron, optical, and scanning probes. The experimental methods and operating principles, especially the in situ cell designs, are described in detail. Representative studies of the in situ/operando techniques are summarized, and finally the major current challenges and future opportunities are discussed. Several important battery challenges are likely to benefit from these in situ/operando techniques, including the inhomogeneous reactions of high‐energy‐density cathodes, the development of safe and reversible Li metal plating, and the development of stable SEI. Recent developments of the five important in situ/operando characterization categories for lithium battery research are summarized, including X‐ray, electron, neutron, optical, and scanning probe techniques. For each technique, the operating principles and in situ cell design are described in detail, including representative studies of typical electrode materials and related processes summarized in tables for easy comparison and cross reference.