Throughout this account, the unique strengths of photochemical and electrochemical approaches toward modulating Ni-catalysishave been demonstrated. While the literature is replete with several reports of unique transformations leveraging both tactics, it is still unclear how to choose an appropriate mode of activation. This is especially the case in drug discovery as medicinal chemistry is often performed across the entire span of electron-rich benzenes and electrondeficient heterocycles with a wide range of different alkyl and heteroatomic fragments. Over the past decade, several strategies towards C(sp 2 )-C(sp 3 ), C(sp 3 )-C(sp 3 ), and C-heteroatom , 100-101, 107, 136-142 cross-couplings have been enabled by photo-and electrochemistry. Throughout our experience in developing Nicatalyzed photo-and electrochemically-driven C-C and Cheteroatom cross couplings, we, as well as others, have noticed several reactivity trends. To aid the community in discerning the appropriate tactic, we have assembled a user guide to help navigate photo-and electrochemically-driven cross-coupling reactions as well as to highlight useful technologies developed by others in the field (Figure ).