Coherent multidimensional electronic spectroscopy can be employed to unravel various channels in molecular chemical reactions. This approach is thus not limited to analysis of energy transfer or charge transfer (i.e. processes from photophysics), but can also be employed in situations where the investigated system undergoes permanent structural changes (i.e. in photochemistry). Photochemical model reactions are discussed by using the example of merocyanine/spiropyran‐based molecular switches, which show a rich variety of reaction channels, in particular ring opening and ring closing, cis–trans isomerization, coherent vibrational wave‐packet motion, radical ion formation, and population relaxation. Using pump‐probe, pump‐repump‐probe, coherent two‐dimensional and three‐dimensional, triggered‐exchange 2D, and quantum‐control spectroscopy, we gain intuitive pictures on which product emerges from which reactant and which reactive molecular modes are associated. Two dimensions provide more insight than one: Coherent electronic multidimensional spectroscopy in different variations allows the separation of photochemical reaction channels. This is demonstrated exemplarily for a molecular switch capable of light‐induced ring‐opening and ring‐closure reactions, cis–trans isomerization, vibrational wave‐packet dynamics, radical cation formation, and population relaxation.