For a molecular electronics technology to be fully serviceable, switching functions will be indispensable. Specifically, it will be desirable to control the conductivity of a given molecule using an external stimulus. This tutorial review discusses photoswitchable mixed valence systems that are comprised of a reversibly photoisomerizable bridging unit connecting two redox-active moieties, and as such represent some of the most simple chemical systems in which switching of charge delocalization can be explored. As photoisomerizable units, dithienylethenes have received much attention in the context of photoswitchable mixed valence, but there are also more exotic examples such as norbornadiene- and dimethyldihydropyrene-based switchable systems. As redox-active units responsible for the mixed valence phenomenon, both metal-containing as well as purely organic moieties have been employed. Typical investigations in this area involve the comparison of cyclic voltammograms and (near-infrared) optical absorption spectra of the two isomeric forms of a given system. The magnitude of the comproportionation constant and evaluation of intervalence absorption bands using appropriate theoretical models yield information regarding the extent of charge delocalization in the two isomeric forms. In several of the compounds investigated so far, the light stimulus induces a substantial increase of charge delocalization, or in the terminology commonly used in mixed valence chemistry, a changeover from class I to class II or even class III behavior.