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.