Nucleophilic vinylic substitution (S(N)V), in which a leaving group such as halogen is replaced by a carbon, oxygen, nitrogen, sulfur, or other nucleophile, is an important synthetic tool. It generates compounds with a carbon- or heteroatom-substituted carbon-carbon double bond, such as vinyl ethers, enamines, a variety of heterocyclic systems, and intermediates to pharmaceutically important compounds. The S(N)V reaction has many mechanistic variants, which depend on the substituents, nucleophile, leaving group, and solvent, among other factors. Among these mechanisms, the "addition-elimination" S(N)V route is the most important to synthetic chemists. S(N)V reactions are involved in several biological processes, notably (i) in the inactivation of proteases, (ii) in intermediates of herbicide metabolism, and (iii) in the formation of mutagenic intermediates by reaction of glutathione with the environmental pollutant trichloroethylene. A variant involving a tetrahedral intermediate was found in the enzymatic transfer of an enolpyruvyl group of phosphoenolpyruvate. The main S(N)V mechanism was previously analyzed in terms of a variable transition state with perpendicular nucleophilic attack. Electron-withdrawing groups Y and Y' in the beta position adjacent to the C(alpha) reaction site increase the nucleophilic attack rate; the retention of stereochemistry was mostly ascribed to formation of carbanionic intermediate 1, in which internal rotation is slower than nucleofuge expulsion (k2). As predicted, poor nucleofuges and high activation led to partial or complete stereoconvergence, and an intramolecular element effect in polyhaloethylenes gave competition ratios, kF/kBr1. Evidence for a zwitterionic intermediate comes from amine-catalyzed substitutions with amines. The mechanistic spectrum investigated is wide in terms of rate constants, electron-withdrawing groups, nucleophiles, leaving groups, and solvents. However, the two extremes, that is, the very slightly activated systems where in-plane invertive substitution is feasible and conversely the highly activated systems carrying poor nucleofuges where the intermediate may be observable and kinetics examined, remained almost unexplored for a long time. In this Account, we describe the progress during the last two decades in these areas. Computations on low-reactivity systems showed that the in-plane invertive single-step nucleophilic sigma attack can have a lower barrier than the pi-perpendicular retentive attack. A kBr/kCl1 could be deduced for the H2C=CHX (X = Cl, Br) system. Several inverted substitution-cyclizations or inverted ring openings were observed. Alkenyl iodonium salts with superb nucleofuges, showed in-plane substitutions by various nucleophiles. In parallel, we demonstrated that several highly activated systems carrying poor nucleofuges enabled a direct detection of the intermediate 1 when attacked by strong nucleophiles. Poor correlation between the equilibrium constants K1(RS) for RS- attack and pKa(CH2YY') indicates large nucleofuge steric effects (SPrSMeOMeH). Rate and equilibrium constants for RS- attack as a function of YY' also correlate poorly owing to differences in intrinsic barriers caused by different resonance effects of YY'. The expulsion of either the nucleofuge (k2) or the nucleophile (k(-1)) from 1 was analyzed with respect to several factors. Challenges still remain, including acquiring experimental data for unactivated systems and observing an intermediate carrying a good nucleofuge.