The outstanding tribological performance of transition metal dichalcogenides (TMDs) is attributed to their unique sandwich microstructure and low interlayer shear stress. This advantageous structure allows TMDs to demonstrate exceptional friction reduction properties. Furthermore, the incorporation of TMDs and amorphous carbon (a-C) in multi-layer structures shows excellent potential for further enhancing tribological and anti-oxidation properties. Amorphous carbon, known for its high ductility, chemical inertness, and excellent wear resistance, significantly contributes to the overall performance of these multi-layer coatings. To gain an in-depth understanding of the tribological mechanism and evolution of TMDs’ multi-layer coatings, a dual in-situ analysis was carried out using a tribometer equipped with a 3D laser microscope and a Raman spectrometer. This innovative approach allowed for a comprehensive evolution of the tribological, topographical, and tribochemical characteristics of both single-layer WS2 and multi-layer WS2/C coatings in real time. The findings from the dual in-situ tribotest revealed distinct failure characteristics between the single-layer WS2 coating and the multi-layer WS2/C coating. The single-layer WS2 coating predominantly experienced failure due to mechanical removal, whereas a combination of mechanical removal and tribochemistry primarily influenced the failure of the multi-layer WS2/C coating. The tribological evolution process of these two coatings can be classified into four stages on the basis of their tribological behavior: the running-in stage, stable friction stage, re-deposition stage, and lubrication failure stage. Each stage represents a distinct phase in the tribological behavior of the coatings and contributes to our understanding of their behavior during sliding.