On the basis of the established electrofugality scale developed for the benzhydrylium system and measured solvolytic rate constants, it is possible to define nucleofugalities of various leaving groups according to the LFER equation log k = sf(Nf + Ef). Electrofugality parameter (Ef) defines heterolytic reactivity of the cationic part of substrates, whereas nucleofugality parameters (Nf and sf) define the reactivity of a leaving group in the combination with employed solvent. Following syntheses of benzhydrylium derivates, nucleofugalities of variously substituted phenolates, benzoates and other carboxylates in combinations with different solvents have been determined. Hereby, the existing nucleofugality scale is supplemented with new leaving groups different in type and structure. In addition, impacts of structural and solvation effects on both nucleofugalities of leaving groups and overall heterolytic reactivities of substrates undergoing solvolysis have been investigated. Despite the differences in the structures and stabilization effects that govern the solvolytic reactivities of invastegated substrates, this LFER model demonstrates both sustainability and consistency in relating the solvolytic reactivity with a structure. In order to supplement the nucleofugality scale with new data, the possibilities of correlating the experimental free energies of activation with activation energies afforded by quantumchemical models have been investigated.