All-carbon graphdiyne (GDY)-based materials have attracted extensive attention owing to their extraordinary structures and outstanding performance in electrochemical energy storage. Straightforward insights into the interfacial evolution at GDY electrode/electrolyte interface could crucially enrich the fundamental comprehensions and inspire targeted regulations. Herein, in situ optical microscopy and atomic force microscopy monitoring of the GDY and N-doped GDY electrodes reveal the interplay between the solid electrolyte interphase (SEI) and Li deposition. The growth and continuous accumulation of the flocculent-like SEI is directly tracked at the surface of GDY electrode. Moreover, the nanoparticle-shaped SEI homogeneously propagates at the interface when N configurations are involved, providing a critical clue for the N-doping effects of stabilizing interfaces and homogenizing Li deposition. This work probes into the dynamic evolution and structure-reactivity correlation in detail, creating effective strategies for GDY-based materials optimization in lithium-ion batteries.