Carburization in Ni-Cr-Fe-based alloys is an important phenomenon, especially in ethylene cracking tubes which serve at high temperatures under highly carburizing environment. In this work, the Cr35Ni45Nb tube subjected to service condition for 6 a was carburized by low-pressure vacuum carburizing (LPVC) at 1080 ℃. The carburization behaviors and corresponding mechanisms of phase evolution in the inner wall were comprehensively analyzed through SEM, XRD and EPMA. The results showed that oxidation behaviors of the tube at high temperature were consisted of external oxidation of Cr and internal oxidation of Si, resulting in formation of composite oxide scales. Depletion of Cr in the subsurface caused by surface Cr₂O₃ leaded to carbide dissolution and formation of carbide free zone and carburized zone. The critical concentration of Cr for carbide dissolution is about 19.0% (mass fraction). By comparing carburization behaviors of specimens whose oxide scales were retained or removed, the carburization resistance of the composite oxide scales in carburizing environment was systematically investigated. The results showed that the composite oxide scales formed previously acted as an effective barrier to carbon infiltration. However, the outermost Cr₂O₃ scale tended to be carbonized to form carbide scale to spall from the surface in the strongly reducing environment with low oxygen partial pressure, while the SiO₂ kept stable all along due to its excellent thermodynamic stability. However, a certain amount of carbon was still capable to penetrate the alloy interior through gaps of the SiO₂ scale due to its discontinuity. Therefore, continuity, density and high-temperature stability of the oxide scales were crucial for the alloy to achieve excellent anti-carburizing performance. Once the oxide layers were removed or carbonized adequately, inconceivable internal carburization occured widely. Large amounts of secondary carbides precipitated again in the previous carbide free zone due to high carbon activity. Widespread precipitations of graphite called metal dusting in the range of about 0.5 mm in depth occurred after long exposure of specimens to the carburizing environment. The carbon activity gradually decreased with increasing distance from the surface. The primary carbides within the deeper carburized region were transformed from M₂₃C₆ to M₇C₃ in situ, which were accompanied by precipitation of vermicular g phase in the primary carbides, phase transition from h to NbC and decomposition of intragranular secondary carbides. Severe coalescing and coarsening of carbides and metal dusting caused the serious degradation of microstructure, formation of macro-cracks and final thinning of the Cr35Ni45Nb tube wall.