The mechanism and the stereochemistry of the intracomplex "solvolysis" of the proton-bound complexes I-X between (CH3OH)-O-18 and (R)-(+)-1-aryl-ethanol (1(R)(X); aryl = phenyl (X = H); pentafluorophenyl (X = F)) have been investigated in the gas phase in the 25-100 degreesC temperature range. The results point to intracomplex "solvolysis" as proceeding through the intermediacy of the relevant benzyl cation IIIX (a pure S(N)1 mechanism), "Solvolysis" of I-H leads to complete racemization at T > 50 degreesC, whereas at T < 50 C the reaction displays a preferential retention of configuration. Predominant retention of configuration is also observed in the intracomplex "solvolysis" of I-F. This picture is rationalized in terms of different intracomplex interactions between the benzylic ion IIIX and the nucleophile/leaving group pair, which govern the timing of their reorientation within the electrostatic complex. The obtained gas-phase picture is discussed in the light of related gas-phase and solution data. It is concluded that the solvolytic reactions are mostly governed by the lifetime and the dynamics of the species involved and, if occurring in solution, by the nature of the solvent cage. Their rigid subdivision into the S(N)1 and S(N)2 mechanistic categories appears inadequate, and the use of their stereochemistry as a mechanistic probe can be highly misleading.