The merger of photochemical and electrochemical technologies with transition metal catalysis has led to a watershed of new tools for the synthetic community that would have otherwise been impossible a decade ago. The powerful nature of these redox tools to coax elusive reactivity out of first-row transition metals has been highlighted throughout our efforts in C-C and C-heteroatom cross-couplings. By comparing the mechanistic and substrates scope features of the two strategies, chemical practitioners can form a strong basis upon which mode of activation is best fit for a proposed synthetic target with the assistance of a tactical guide. The practical utility of redox control enacted by photochemistry and electrochemistry is compelling and will certainly grow as a tool for developing more powerful transformations so long as efforts in understanding the mechanistic underpinnings of the current limitations are undertaken. We hope that this account inspires the next generation of researchers to confront fundamental challenges in first-row transition metal catalysis through cross-disciplinary collaborative efforts.