We have reviewed electronic structure methods for describing the influence of the electrode potential in semiconductor electrochemistry. First, we discussed the formal definition of electrode potential as the bulk Fermi level or inner potential. Then, we addressed in detail which physicochemical features complicate the DFT modelling of semiconductor electrodes -these are collected in Figure . We emphasized the difficulty and importance of including various defect states and the space-charge region in electronic structure calculations. In particular, without accurate models of the SCR, one cannot model the semiconductor bulk and thereby define the electrode potential.