The feasibility of the direct lithiation of monohydric compounds (such asa secondary benzamide, phenol, and thiophenol) and dihydric and trihydric phenols has been theoretically examined by using the semiempirical MNDO method. MNDO-determined agostic interaction parameters and proximity features show an outstanding capacity in qualitatively predicting the closeness of the corresponding transition states. According to these parameters, peri lithiation of mono- or polyhydric phenolic compounds (whenever possible) should be kinetically favored over alternative processes. Even second peri lithiations appear to be achievable objectives on account of these indicators. These prognostications have been borne out by experiment for the first time as dihydric phenols of the naphthalene, anthracene, and phenanthrene series yielded peri-substituted products on treatment with nBuLi in N,N,N’,N’-tetramethylethylenediamine (TMEDA) as solvent, followed by quenching with common electrophiles. Double peri functionalized derivatives of several dihydroxynaphthalenes and phenanthrenes were obtained by directed lithiation of the unprotected compounds. These results strongly suggest the key role that agostic interaction plays on directed lithiations and provide indirect evidence for the intermediacy of such precoordinated species in these reactions.