Ligand-to-metal charge transfer (LMCT) photocatalysis has emerged into a powerful tool to easily access reactive electrophilic radicals from abundant and inexpensive metal complexes enabling diverse reactivity. Light absorption by a LMCT band induces a homolytic cleavage of a metal-ligand bond resulting in a reduced metal complex and an oxidized ligand radical. Even though these photophysical principles were never restricted to certain metals, modern synthetic applications have been limited mostly to cerium and its alkoxy and carboxyl radical chemistry. The recent utilisation of chlorine radicals generated from copper and iron salts serving as hydrogen atom abstractors expanded the portfolio of LMCT applications to C-H bond functionalisation of various hydrocarbons. In these transformations, the bond homolysis of a catalyst complex circumvents the requirements for long excited state lifetimes and matching redox potentials between substrate and catalyst thus allowing complementary reactivity patterns to classical single electron transfer (SET) catalysis. Comparing the different LMCT complexes it becomes obvious that the metal character is crucially influencing, enabling and disabling certain reactivity modes. Benzoic acids, for example, while being utilized as fully recoverable ligands in synergistic cerium catalysis, readily undergo decarboxylation as copper-substrate complexes yielding phenyl radicals after excitation. Moreover, unique reaction outcomes are achieved when a single metal fulfils multiple roles besides LMCT activation. Of course, this behaviour is linked to specific elements -as an example efficient photocatalytic radical oxidation enabling crossnucleophile coupling has so far only been achieved with copper. Furthermore, the Doyle group demonstrated an intriguing combination of LMCT with multiple transition metal catalysis steps orchestrated by a single nickel catalyst. Despite these impressive developments, this research field is still in its infancy and new synthetic opportunities are to be discovered by expanding LMCT to different metal catalysis platforms.