SiOx electrodes are promising for high-energy-density lithium-ion batteries (LIBs) due to their ability to mitigate volume expansion-induced degradation. Here, we investigate the surface dynamics of SiOx thin-film electrodes cycled in different carbonate-based electrolytes using a combination of ex situ X-ray photoelectron spectroscopy (XPS) and operando synchrotron X-ray reflectivity analyses. The thin-film geometry allows us to probe the depth-dependent chemical composition and electron density from surface to current collector through the solid electrolyte interphase (SEI), the active material, and the thickness evolution during cycling. Results reveal that SiOx lithiation initiates below 0.4 V vs Li+/Li and indicate a close relationship between SEI formation and SiOx electrode lithiation, likely due to the high resistivity of SiOx. We find similar chemical compositions for the SEI in FEC-containing and FEC-free electrolytes but observe a reduced thickness in the former case. In both cases, the SEI thickness decreases during delithiation due to the removal or dissolution of some carbonate species. These findings give insights into the (de)lithiation of SiOx, in particular, during the formation stage, and the effect of the presence of FEC in the electrolyte on the evolution of the SEI during cycling.