The SN2 reaction of F− + CH3Cl covers a conducive energy domain described by its potential energy surface with varied ∠FCCl and CF distance. Loci of the potential energy surface produce two reaction wells, one is due to nonconventional F∙∙∙HC hydrogen bonding and the other is due to linear backside attack. The effect of solvent polarity on the PESs leads to (i) a significant increase in the energy barrier of the reaction with increase in the polarity of the solvent, (ii) disappearance of the transition state between the reaction complexes formed due to hydrogen bonding and direct attack on the carbon atom in the polar solvents, and (iii) the formation of reactant complex in cyclohexane due to direct attack of the nucleophile, while in toluene, the complex formation is due to hydrogen bond interaction.