AbstractThe dynamics of the structural changes in the electrochemical double layer at the interface between a Ag(111) electrode and 0.1 M KOH electrolyte have been probed using surface X‐ray diffraction measurements. The X‐ray measurements utilised a lock‐in amplifier technique to obtain a time resolution down to the millisecond scale. Two potential step regions were explored in an attempt to separate the dynamics of the reversible adsorption/desorption of hydroxide species (OHad) and the subsequent cation (K+) ordering in the double layer. By probing different positions in reciprocal space, sensitive to different structural changes, the time‐dependent response of the electrode surface was probed and time constants for the different associated processes were obtained.