The chemical modification of electrodes with organic materials is a common approach to tuning the electronic and electrostatic landscapes between interlayers in optoelectronic devices, thus facilitating charge injection at the electrode/semiconductor interfaces and improving their performance. The use of photochromic molecules for surface modification allows a dynamic control of the electronic and electrostatic properties of the electrode and thereby enables additional functionalities in such devices. Here, we show that the electronic properties of a transparent indium–tin oxide (ITO) electrode are reversibly and dynamically modified by depositing organic photochromic switches (diarylethenes) in the form of self-assembled monolayers (SAMs). By combining a range of surface characterization and density functional theory calculations, we present a detailed picture of the SAM binding to ITO, the packing density of …