Cleavage of an Aryl–Leaving Group bond (Ar–LG) is the key step in most arylation processes for the synthesis of highly functionalized (hetero)arenes. In metal‐free arylations, depending on the nature of the starting substrates, different thermal and photochemical approaches can be adopted: Single Electron Transfer (SET) and homolysis/heterolysis of an Ar–LG bond to afford an aryl radical (Ar·) or an aryl cation (Ar+), respectively. Accordingly, the nature of LG plays a key‐role in determining the mechanism and efficiency of the process.