We present a systematic characterization of the transition layer at the 4H-SiC/SiO 2 interface as a function of nitric oxide (NO) post-annealing time, using high-resolution transmission electron microscopy for structural characterization and spatially resolved electron energy-loss spectroscopy for chemical analysis. We propose a systematic method for determining transition layer width by measuring the monotonic chemical shift of the Si-L 2,3 edge across the interface, and compare its efficacy to traditional measures from the literature, revealing the proposed method to be most reliable. A gradual shift in the Si-L 2,3 edge onset energy suggests mixed Si-C/Si-O bonding in the transition layer. We confirm an inverse relationship between NO-anneal time and transition layer width, which correlates with improved channel mobility, enhanced N density at the interface, and decreased interface trap density. No excess C was noted in the interfacial region. V