We started to investigate the potential of simple bench stable metal chlorides available in our laboratories (Figure ). A relatively high metal chloride loading (35 mol%) was selected to spot also minor LMCT activity. A set of differently coordinating solvents was used as their coordination has been proven to be beneficial in some cases (e.g., copper). One set of conditions used additional chloride ligand to allow the formation of highly coordinated carboxylate, or mixed carboxylate-chloride complexes. Higher coordination generally improves absorption properties as demonstrated in the case of copper and cerium (e.g., CuCl 3 -, FeCl 4 ). Based on previous reports, 375 nm LEDs were used, because they excite synthetically useful LMCT absorption bands. These bands typically appear higher than 300 nm and tail towards the visible region. To verify the developed screening assay, cerium and iron chlorides were used as positive controls. Indeed, the positive outcome of these two metals made us confident that the selected parameters cover a correct range of conditions enabling LMCT. Moreover, an expected rediscovery of carboxyl radicals from copper complexes in a new transformation gave additional validity to the assay. Taking advantage of the experimental simplicity of this screening, also improbable metal chlorides like AlCl 3 , ZnCl 2 , NbCl 3 , CdCl 2 , InCl 3 and PbCl 2 were tested, and some gave product in detectable amounts. NiCl 2 and CoCl 2 showed no conversion even though their photophysical properties for LMCT were described before. The reason for inactivity is probably that higher oxidation state (III) was not achieved by oxidation with oxygen. Remarkable is the LMCT activity of gold across multiple reaction conditions. We did not further investigate this observation but hope that the reactivity and synthetic use of these complexes will be further investigated in a different context. For us, the biggest surprise and opportunity of the screening is the discovery of the exceptional performance of bismuth chloride as LMCT photocatalyst. This finding expands LMCT activity from transition metal domain to main group element. Moreover, bismuth is inexpensive, non-toxic, and in contrast to 3d metals engaging in catalysis with p-orbitals. Heterogenous bismuthbased materials are already established in environmental and energy photocatalysis and in some synthetic procedures. However, in strong contrast molecular bismuth photoredox catalysis is almost unknown. As pointed out by the Cornella group in their recent perspective, photoredox access to homogenous bismuth catalysis would inherently provide further opportunities to unveil new catalytic cycles and reactions within bismuth catalysis platform. Especially LMCT photocatalysis has potential to become an elegant addition to emerging bismuth catalysis. On one hand LMCT gives access to elusive bismuth (II) intermediates, and on the other hand it forms a useful electrophilic radical (e.g., carboxyl or chlorine radical) in a single excitation event.