Silicon is an important electrode material for the continued manufacturing of Si-based lithium-ion batteries, solar cells and field effect transistors. These types of devices take advantage of silicon’s inherent native oxide layer (SiOx) to produce long-lasting, stable electronic devices. However, researcher often sacrifice this SiOx layer, which provides stability to the electrode, in exchange for the much-improved functionalisation capability of oxide-free silicon. However, my recent work has shown that electrochemical reduction of diazonium salts is facilitated via electron tunnelling through the thin native SiOx layer. My research explored if this electrochemical process was dependent upon the silicon crystal structure via anisotropic etching of Si(100) wafers, simultaneously exposing both the Si(111) and Si(100) faces. Complementing this work, an in-depth study revealed the existence of common background signals on natively oxidised silicon electrodes, monitored by electrochemistry. These reversible redox signals are attributed to a reversible silicon to silica redox reaction at the nanoscale, facilitated by highly conducting Si(111)/Si(110) steps atop Si(111) oriented electrode surfaces. This work serves a dual purpose in highlighting an interesting phenomenon where an inert species (SiOx) undergoes a reversible redox reaction at moderate potentials (approx. +0.2 V / vs Ag/AgCl), while also providing a reference for future researchers to accurately assign these signals in their own work. Further electrical characterisation was conducted using scanning tunnelling microscopy, revealing an interface where current rectification is reliant upon the presence of the SiOx layer. Altogether, this work advances our understanding of the electrochemical and electrical properties of oxidised silicon electrodes, revealing a stable and versatile electrode material with continued relevance in electronics and batteries.