► XPS and ToF-SIMS study of solid electrolyte interphase layer on Si thin film and Si nanowires electrodes is presented. ► Modification of Si electrode surface morphology is evidenced by SEM micrographs. ► Organic part of solid electrolyte interphase is present at the outer- and inorganic part in the innermost surface. ► Different thickness of solid electrolyte interphase is observed in a function of type of electrolytes. The effect of the Si electrode morphology (amorphous hydrogenated silicon thin films – a-Si:H as a model electrode and Si nanowires – SiNWs electrode) on the interphase chemistry was thoroughly investigated by the surface science techniques: X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS analysis shows a strong attenuation and positive shift of the Si 2p peaks after a complete charge/discharge performed in PC- and EC:DMC-based electrolytes for both electrodes (a-Si:H and SiNW), confirming a formation of a passive film (called solid electrolyte interphase – SEI layer). As evidenced from the XPS analysis performed on the model electrode, the thicker SEI layer was formed after cycling in PC-based electrolyte as compared to EC:DMC electrolyte. XPS and ToF-SIMS investigations reveal the presence of organic carbonate species on the outer surface and inorganic salt decomposition species in the inner part of the SEI layer. Significant modification of the surface morphology for the both electrodes and a full surface coverage by the SEI layer was confirmed by the scanning electron microscopy (SEM) analysis.