The invention relates to an electrode structure for in situ observation of a lithium ion diffusion mode in a graphite material. A circular working electrode structure and an annular counter electrodestructure are used to form an edge-to-edge structure in which two electrodes are distributed in the in-plane concentric circle position. The lithium ion diffusion form in the electrodes is in the radial direction of the electrodes. The working electrode thereof is circular, and the counter electrode is annular. The inner diameter of the annular electrode is larger than the outer diameter of the circular electrode. A conductive device uses a copper metal pin with a flange. The upper part is pressed on the electrode material. The lower part is connected with a conductive copper ring to realize the communication between the electrode material and an external wire. According to the invention, the lithium ion diffusion process of the working electrode during an insertion/de-lithium cyclic process can be directly observed in situ; the difficulty of unable measurement caused by a conventional face-to-face electrode method is overcome; the design of the circular electrode is more in line withthe structural design of a commercial electrode; and diffusion evolution in all directions can be studied.