With the increasing demand for electric vehicles, further development of Li batteries require more comprehensive studies and advanced techniques to analyze various battery material and mechanisms. Determining the concentration of Li and electric potential inside batteries can effectively reveal and predict the electrochemical performance, understanding the charge/discharge processes and failure mechanisms. Recently, observation of Li movement have been reported by utilizing optical microscopy, neutron imaging (NI), neutron depth profiling (NDP), and transmission electron microscopy (TEM)-based electron energy-loss spectroscopy (EELS). These extensive works suggest their broad potential applications, including revealing the spatial distribution of Li, mapping electrode elements, and indicating degradation mechanisms. Moreover, direct visualization of potential changes through TEM-based electron holography (EH) and Kelvin probe force microscopy (KPFM) can discover and validate more valuable information. This perspective paper summarizes the current development of advanced techniques for observing Li and potential distribution inside batteries for the first time. Additionally, we address the key challenges faced by these techniques along with their possible solutions. The aim of this paper is to provide a comprehensive discussion of methods for analyzing reaction mechanisms, optimizing electrochemical performance, and potentially supporting the further development of battery simulation.