AbstractThe 2‐dimensional electron gas (2DEG) found at the surface of SrTiO₃ and related interfaces has attracted significant attention as a promising basis for oxide electronics. In order to utilize its full potential, the response of this 2DEG to structural changes and surface modification must be understood in detail. Here, a study of the detailed electronic structure evolution of the 2DEG as a function of sample temperature and surface step density is presented. By comparing the experimental results with ab initio calculations, it is shown that local structure relaxations cause a metal‐insulator transition of the system around 135 K. This study presents a new and simple way of tuning the 2DEG via surface vicinality and identifies how the operation of prospective devices will respond to changes in temperature.