In summary, we developed a screening assay which enables quick identification of dissociative LMCT activity. While we were focusing on simple metal chloride salts, this approach should be readily adoptable to more sophisticated metal complexes. The developed assay revealed LMCT activity of bismuth salts. Simple photo-redox activation provides access to elusive low valent bismuth (II) from bench stable bismuth (III) carboxylate and chloride complexes. The latter was used for redox neutral C-H bond activation in Giese-type coupling reactions. We investigated the faith of elusive bismuth (II) intermediates by combined cyclovoltammetry and spectro-electrochemical measurements. We observed a pronounced bismuth (II) disproportionation and indications of a radical rebound to carbon centred radicals in our reaction system. Future work will focus on a detailed study of photocatalytic generated bismuth carbon radical equilibria and utilization of their synthetic potential.