This study investigates the rich mechanistic landscape of the iconic electrophilic aromatic substitution (EAS) reaction class, in the gas phase, in solvents, and under stimulation by oriented external electric fields. The study uses DFT calculations, complemented by a qualitative valence bond (VB) perspective. We construct a comprehensive and unifying framework that elucidates the many surprising mechanistic features, uncovered in recent years, of this class of reactions. For example, one of the puzzling issues which have attracted significant interest recently is the finding of a variety of concerted mechanisms that do not involve the formation of sigma-complex intermediates, in apparent contradiction to the generally accepted textbook mechanism. Our VB modeling elucidates the existence of both the concerted and stepwise mechanisms and uncovers the root causes and necessary conditions for the appearance of these intermediates. Furthermore, our VB analysis offers insight into the potential applications of external electric fields as smart, green, and selective catalysts, which can control at will reaction rates, as well as mechanistic crossovers, for this class of reactions. Finally, we highlight how understanding of the electric fields effect on the EAS reaction could lead to the formulation of guiding principles for the design of improved heterogeneous catalysts. Overall, our analysis underscores the powerful synergy offered by combining molecular orbital and VB theory to tackle interesting and challenging mechanistic questions in chemistry.